CA2883104A1

CA2883104A1 - Method for processing hydrocarbon oil and apparatus for processing hydrocarbon oil

Info

Publication number: CA2883104A1
Application number: CA2883104A
Authority: CA
Inventors: Tomoki Kayukawa; Takayoshi Fujimoto; Shigeki Nagamatsu; Tomoyuki Hirao; Shinichiro Yanagawa
Original assignee: JGC Corp; JX Nippon Oil and Energy Corp
Current assignee: JGC Corp; Eneos Corp
Priority date: 2012-10-03
Filing date: 2013-09-17
Publication date: 2014-04-10
Anticipated expiration: 2033-09-17
Also published as: WO2014054234A1; RU2617846C2; RU2015115923A; JP2014074111A; CO7270467A2; CA2883104C

Abstract

A method for processing a hydrocarbon oil and an apparatus for processing a hydrocarbon oil, with which the olefin or diene content in the hydrocarbon oil can be reduced even in the case where it is difficult to obtain hydrogen are provided.
[Means for Resolution]
Water and a hydrocarbon oil containing at least one of a diene and an olefin are brought into contact with a cracking catalyst at a temperature of 375 to 550°C to effect cracking, thereby producing a cracked hydrocarbon oil and hydrogen, and then, the hydrogen and the cracked hydrocarbon oil are brought into contact with a hydrogenation catalyst at a temperature of 100 to 374°C to effect a hydrogenation reaction of the cracked hydrocarbon oil, thereby reducing the content of at least one of the diene and the olefin.

Description

[Designation of Document] SPECIFICATION
[Title of the Invention] METHOD FOR PROCESSING HYDROCARBON OIL
AND APPARATUS FOR PROCESSING HYDROCARBON OIL
[Technical Field]
[0001]
The present invention relates to a technique for reducing an olefin or a diene contained in a hydrocarbon oil.
[Background Art]

[0002]
While it is expected that demand for a crude oil will be increasing primarily in developing countries such as China and India in the future, the production of a light crude oil which has been conventionally used is reaching a peak, and therefore, necessity of use of a heavy crude oil or an extra-heavy crude oil, which has not been used much so far, is increasing. Among extra-heavy crude oils, as for Canadian oil sand bitumen and Venezuelan orinoco tar, their economical production processes have already been established, and the production amounts thereof are increasing.

[0003]
The density and viscosity of such an extra-heavy crude oil are very high, and therefore, in order to transport it from an oil well in a producing region to an oil refinery in a consuming region, the extra-heavy crude oil cannot be transported as such using a pipeline or the like. Due to this, f at a well site, the following two methods are selected: a dilution method in which a diluent is mixed therein to decrease the viscosity; and a upgrading method in which a light synthetic crude oil is produced by constructing a plant called an upgrader nearby.

[0004]
However, the dilution method has a problem that a diluent such as a condensate should be sufficiently ensured or a problem that since the transport amount is increased by the amount of dilution, the transport cost is increased. Further, also in the upgrading method, a problem that since a large-scale plant equivalent to that in an oil refinery is needed in a well site, only the vicinity of a large oil field is economically justified, a problem that by-products such as coke and sulfur should be treated, or a problem that hydrogen required for the upgrading should be ensured may sometimes arise.

[0005]
In light of these problems, the present inventors have developed a technique for producing a synthetic crude oil which can be transported through a pipeline without resort to a diluent by upgrading a heavy crude oil or an extra-heavy crude oil using supercritical water according to a simple scheme at a well site. However, the synthetic crude oil produced here has undergone heat history, so that a hydrocarbon in the oil is cracked or the like, and therefore an unsaturated hydrocarbon is produced, resulting in increasing the concentration of an olefin or a diene. If the concentration of an olefin or a diene is high, the stability of the oil is low, and polymerization or the like occurs during transport, and thus, there is a risk to cause a problem such as deposition of the polymerized product in the pipeline or clogging of the pipeline with the polymerized product. Therefore, for example, in Canada, the olefin concentration is defined to be 1% or less in the specification of the pipeline. Such an olefin or a diene can be reduced by a hydrogenation reaction, however, it is necessary to ensure hydrogen therefor. In the case where there is no hydrogen production facility nearby as in a well site and it is difficult to obtain hydrogen, generally, a necessity arises that a facility for producing hydrogen using natural gas or naphtha as a raw material should be constructed. However, the construction of such a hydrogen production facility leads to an increase in construction cost, and also has a problem that it is difficult to obtain natural gas or naphtha to be used as a raw material in some regions, or the like.

[0006]
On the other hand, in the oil refinery, a cracked oil produced by an FCC unit or a coker unit has a relatively high olefin concentration, and such an olefin forms sludge in a transport pipe or a refined oil tank, and therefore may cause clogging or the like. Due to this, it may sometimes be =
necessary to remove olefin components in the cracked oil, =
however, purification by hydrogenation in the conventional method has a problem that the in-house utility hydrogen is consumed.

[0007]
In PTL 1 to PTL 3, a technique for converting a hydrocarbon oil into a light oil with respect to a mixture of a hydrocarbon oil and water by allowing a cracking reaction of the hydrocarbon oil to proceed in the presence of a catalyst or under a supercritical water condition is described, however, a technique related to processing of a hydrocarbon oil containing an olefin or a diene is not described.
[Citation List]
[Patent Literature]

[0008]
[PTL 1] Japanese Patent Application Laid-Open Publication No. 2008-297466, Claim 1, Paragraph [0017]
[PTL 2] Japanese Patent Application Laid-Open Publication No. 2009-242467, Claim 1, Paragraph [0028]
[PTL 3] Japanese Patent Application Laid-Open Publication No. 2006-7151, Claim 1, Paragraphs [0017], [0009]
to [0010]
[Summary of Invention]
[Technical Problem]

[0009]

r , = The present invention has been made in view of the above -circumstances, and an object of the invention is to provide a method for processing a hydrocarbon oil and an apparatus for processing a hydrocarbon oil, with which the diene or olefin content in the hydrocarbon oil can be reduced even in the case where it is difficult to obtain hydrogen.
[Solution to Problem]

[0010]
The method for processing a hydrocarbon oil according to the invention is characterized by including:
a step of producing a cracked hydrocarbon oil and hydrogen by bringing water and a hydrocarbon oil containing at least one of a diene and an olefin into contact with a cracking catalyst at a temperature of 375 to 550 C to effect cracking;
and a step of reducing the content of at least one of the diene and the olefin by bringing the hydrogen and the cracked hydrocarbon oil into contact with a hydrogenation catalyst at a temperature of 100 to 374 C to effect a hydrogenation reaction of the cracked hydrocarbon oil.

[0011]
The method for processing a hydrocarbon oil may have the following characteristics.
(1) The method further includes a step of separating water from a mixture containing the cracked hydrocarbon oil C
.
and water after the contact with the cracking catalyst, and the hydrogenation reaction is performed for the cracked hydrocarbon oil after separating water.
(2) The hydrocarbon oil contains upgraded oil obtained by upgrading a feedstock oil using water, and water to be used for producing hydrogen by the cracking catalyst is water discharged along with the upgraded oil. Further, the hydrocarbon oil contains a upgraded oil obtained by bringing a feedstock oil into contact with supercritical water. Still further, the hydrocarbon oil contains at least one fraction obtained by separating the upgraded oil into a plurality of fractions having different boiling point ranges through distillation.
(3) The hydrogenation reaction is performed such that when the ratio of the amount of hydrogen bonded to a terminal carbon-carbon double bond of the diene or the olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by A and the ratio of the amount of hydrogen bonded to an internal carbon-carbon double bond of the diene or the olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by B, the value of A/B falls within a range of 0 to 0.5.
(4) The cracking catalyst is a composite metal oxide, which contains:

= CA 02883104 2015-02-25 = (a) one element X selected from Group IVA elements;
=
(b) one element Y1 selected from the group consisting of Group IIIA elements, Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y1 is an element different from the element X) ; and (c) one element Y2 selected from the group consisting of Group IIIA elements, Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y2 is an element different from the element X and the element Y1), and in which (d) the ratio of the abundance x of the element X to the sum (yi-Fy2) of the abundance yi of the element Y1 and the abundance y2 of the element Y2 is 0.5 or more and 2.0 or less, and (e) the ratio of the abundance y2 of the element Y2 to the abundance yi of the element Y1 is 0.02 or more and 0.25 or less.
For example, the element X is Zr, the element Y1 is Ce, and the element Y2 is an element selected from a Y2 element group consisting of W, Fe, and Mn.
(5) The hydrogenation catalyst is configured such that a metal having a hydrogenation activity is carried on a support composed of a metal oxide which does not include alumina or = silica. For example, the hydrogenation catalyst is configured such that at least one metal selected from the group consisting of nickel, cobalt, and molybdenum is carried on a support containing zirconia or anatase-type titania.

[0012]
Next, the apparatus for processing a hydrocarbon oil according to another aspect of the invention is characterized by including:
a cracking reactor, which is supplied with water and a hydrocarbon oil containing at least one of a diene and an olefin, and is packed with a cracking catalyst which produces a cracked hydrocarbon oil and hydrogen from the hydrocarbon oil and the water; and a hydrogenation reactor, which is supplied with the hydrogen produced in the cracking reactor and the cracked hydrocarbon oil flowing out of the cracking reactor, and is packed with a hydrogenation catalyst which reduces the content of at least one of the diene and the olefin by allowing a hydrogenation reaction of the cracked hydrocarbon oil to proceed.

[0013]
The apparatus for processing a hydrocarbon oil may have the following characteristics.
(6) The apparatus further includes an oil-water separator tank which separates water from a mixture containing i =
-water and the cracked hydrocarbon oil flowing out of the cracking reactor, and to the hydrogenation reactor, the cracked hydrocarbon oil after separating water in the oil-water separator tank is supplied.
(7) The hydrocarbon oil contains upgraded oil obtained from a upgrading apparatus which upgrades a feedstock oil using water, and water to be used for producing hydrogen by the cracking catalyst is water discharged along with the upgraded oil. Further, the hydrocarbon oil contains a upgraded oil obtained from a supercritical water upgrading apparatus which upgrades a feedstock oil by bringing the feedstock oil into contact with supercritical water. Still further, the hydrocarbon oil contains at least one fraction obtained from a distillation apparatus which separates the upgraded oil into a plurality of fractions having different boiling point ranges through distillation.
(8) The hydrogenation reaction is performed such that when the ratio of the amount of hydrogen bonded to a terminal carbon-carbon double bond of the diene or the olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by A and the ratio of the amount of hydrogen bonded to an internal carbon-carbon double bond of the diene or the olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by B, the value of A/B falls within a range of - * 0 to 0.5.
(9) The cracking catalyst is a composite metal oxide, which contains:
(a) one element X selected from Group IVA elements;
(b) one element Y1 selected from the group consisting of Group IIIA elements, Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y1 is an element different from the element X); and (c) one element Y2 selected from the group consisting of Group IIIA elements, Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y2 is an element different from the element X and the element Y1), and in which (d) the ratio of the abundance x of the element X to the sum (yi-i-y2) of the abundance yi of the element Y1 and the abundance y2 of the element Y2 is 0.5 or more and 2.0 or less, and (e) the ratio of the abundance y2 of the element Y2 to the abundance yi of the element Y1 is 0.02 or more and 0.25 or less.
(10) The hydrogenation catalyst is configured such that a metal having a hydrogenation activity is carried on a support composed of a metal oxide which does not include alumina or A
silica.
[Advantageous Effects of Invention]

[0014]
According to the invention, by using hydrogen produced by bringing water and a hydrocarbon oil containing a diene or an olefin into contact with a cracking catalyst, a hydrogenation reaction of a cracked hydrocarbon oil obtained along with this hydrogen is performed, and therefore, even in a situation where it is difficult to obtain hydrogen, a cracked hydrocarbon oil having a reduced diene or olefin content can be obtained. Further, the amount of hydrogen to be produced can be adjusted according to the diene or olefin content in the hydrocarbon oil to be processed.
[Brief Description of Drawings]

[0015]
[Fig. 1] Fig. 1 is an explanatory view showing the outline of a process to which the invention is applied.
[Fig. 2] Fig. 2 is a process flow diagram showing a first configuration example of a processing apparatus according to an embodiment of the invention.
[Fig. 3] Fig. 3 is a process flow diagram showing a second configuration example of the processing apparatus.
[Fig. 4] Fig. 4 is a process flow diagram showing a third configuration example of the processing apparatus.
[Fig. 5] Fig. 5 is a process flow diagram showing an example in which the processing apparatus is combined with a supercritical water upgrading apparatus.
[Fig. 6] Fig. 6 is a first explanatory view showing the results of an Example.
[Fig. 7] Fig. 7 is a second explanatory view showing the results of an Example.
[Fig. 8] Fig. 8 is a third explanatory view showing the results of an Example.
[Fig. 9] Fig. 9 is a fourth explanatory view showing the results of an Example.
[Fig. 10] Fig. 10 is a fifth explanatory view showing the results of an Example.
[Fig. 11] Fig. 11 is a sixth explanatory view showing the results of an Example.
[Fig. 12] Fig. 12 is a seventh explanatory view showing the results of an Example.
[Description of Embodiments]

[0016]
[Hydrocarbon oil]
An embodiment of the invention is applied to a hydrocarbon oil containing at least one of an olefin having one carbon-carbon double bond (hereinafter simply referred to as a double bond) and a diene having two double bonds in the molecular structure of the hydrocarbon. The hydrocarbon may be a chain hydrocarbon, a naphthenic hydrocarbon, or an aromatic hydrocarbon. In the case of a chain hydrocarbon, the hydrocarbon may have a double bond in the carbon backbone, or may have a double bond in a side chain. In the case of a naphthenic hydrocarbon or an aromatic hydrocarbon, a double bond in a side chain bonded to a naphthenic ring, an aromatic ring, or a fused ring thereof is a target to be processed. In such a hydrocarbon, an atom such as oxygen, nitrogen, or sulfur maybe contained. Incidentally, in the invention, by focusing on a hydrocarbon containing one or two double bonds and having a relatively low molecular weight, it is intended to reduce the double bonds. However, it is a matter of course that the content of double bonds in a hydrocarbon containing three or more double bonds may be reduced accompanying the application of this processing.

[0017]
An olefin or a diene is contained in a hydrocarbon oil having undergone heat history, and the heat history is applied when performing processing by a process or the like of converting a feedstock oil into a light oil by removing or cracking a heavy oil component. Examples of the process accompanying heat history include a coker, FCC (Fluid Catalytic Cracking), Eureka (registered trademark) in which thermal cracking of a feedstock oil is performed in the presence of steam (water), CPJ, aqua conversion, and a supercritical water processing in which a light oil component obtained by bringing a heated feedstock oil into contact with supercritical water to effect thermal cracking is extracted in supercritical water.

[0018]
Examples of the feedstock oil to be processed by such a process include heavy crude oils from the Middle Eastern countries, heavy oils such as an atmospheric residue and a vacuum residue of a heavy crude oil, and extra-heavy crude oils such as Canadian oil sand bitumen and Venezuelan orinoco tar.
Here, a hydrocarbon oil obtained by processing a feedstock oil through a upgrading process such as a supercritical water processing is referred to as a upgraded oil.

[0019]
It is known that in the upgraded oil, for example, a fraction having a distillation temperature of 60 to 220 C has a relatively high olefin or diene content. Such an olefin or a diene can be reduced by a hydrogenation reaction in which a carbon-carbon bond is cleaved, however, as described in the background art, it is often difficult to obtain cheap hydrogen in a upgrading process provided at a well site or the like.
Therefore, the present inventors developed a technique in which hydrogen is generated by a catalytic reaction of a upgraded oil using water which can be easily obtained even at a well site or the like, and an olefin or a diene in the upgraded oil is reduced by a hydrogenation reaction using the generated hydrogen.

' [0020]
[Outline of process]
Figs. 1(a) and 1(b) show a schematic flow diagram of a process according to an embodiment. According to these drawings, water and a upgraded oil containing an olefin or a diene flowing out of a upgrading process 3 are supplied to a cracking reactor 1 and brought into contact with a cracking catalyst, whereby a cracked hydrocarbon oil and hydrogen are produced (a cracking step) . These cracked hydrocarbon oil and hydrogen are supplied to a hydrogenation reactor 2 and brought into contact with a hydrogenation catalyst to effect a hydrogenation reaction, whereby the olefin or diene content is reduced (a hydrogenation step) . The cracked hydrocarbon oil having a low olefin or diene content obtained from the hydrogenation reactor 2 can be used as a raw material of a synthetic crude oil or the like.
The cracking reactor 1 is packed with a cracking catalyst, and the hydrogenation reactor 2 is packed with a hydrogenation catalyst, however, the method for bringing the upgraded oil or the cracked hydrocarbon oil into contact with each catalyst is not limited to the case where such a fluid is passed through a fixed bed, and a favorable method such as a fluidized bed system or an ebullated bed system may be adopted.
[0021]
Here, as shown in Fig. I (a) , in the upgrading process 3 (for example, the above-described CPJ, Eureka, aqua conversion, supercritical water processing, or the like) in which water is used when performing the processing, water supplied to the upgrading process 3 for upgrading processing and then discharged from the upgrading process 3 along with the upgraded oil can be used as water for generating hydrogen.
On the other hand, in the case of the upgrading process 3 in which water is not used (for example, the above-described coker, FCC, or the like), water is supplied to the cracking reactor 1 separately from the upgraded oil from the upgrading process 3 (Fig. 1(b)).
[0022]
[Cracking step]
(Reaction) In the cracking step, a upgraded oil and water are brought into contact with a cracking catalyst to crack the upgraded oil and water, whereby a cracked hydrocarbon oil and hydrogen are obtained. As the reaction of cracking the upgraded oil and water, for example, while the upgraded oil is cracked using lattice oxygen in an oxide contained in the cracking catalyst, water is cracked by incorporating a water cracking catalyst in the cracking catalyst, and a lattice defect is compensated with oxygen. By this cracking of water, hydrogen is generated and these cracked hydrocarbon and hydrogen are transferred to the hydrogenation step.

[0023]
, (Cracking catalyst) As the cracking catalyst for allowing the above-described reaction to proceed, for example, a composite metal oxide which is an oxide obtained by combining two or more metal oxides can be used. Specifically, a composite metal oxide containing given elements X, Yi, and Y2 can be used as the cracking catalyst. The crystal structure of the composite metal oxide to be used as the cracking catalyst can be evaluated using, for example, an X-ray diffraction analysis.
[0024]
As the composite metal oxide containing a given element X, a given element Y1, and a given element Y2, a composite metal oxide containing the following three metal elements:
(a) one element X selected from Group IVA elements;
(b) one element Y1 selected from the group consisting of Group IIIA elements, Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y1 is an element different from the element X) ; and (c) one element Y2 selected from the group consisting of Group IIIA elements, Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y2 is an element different from the element X and the element ' Y1) at a given ratio can be exemplified.
-[0025]
Here, as the "given ratio", for example, the ratio (molar ratio) of the abundances of the respective elements X, Y1, and Y2 in the catalyst as determined by a melting/ICP-AES method can be exemplified as follows:
(d) the ratio of the abundance x of the element X to the sum (yi-Fy2) of the abundance yi of the element Y1 and the abundance y2 of the element Y2 is 0.5 or more and 2.0 or less (0.5 x/(yi-Ey2) 2.0) , and (e) the ratio of the abundance y2 of the element Y2 to the abundance yi of the element Y1 is 0.02 or more and 0.25 or less (0.02 y2/yi 0.25).
[0026]
The composite metal oxide to be used as the cracking catalyst is not limited to specific elements as long as it meets the above-described requirements, however, specific examples of the element X, the element Y1, and the element Y2 include Ti, Zr, Ce, W, Mn, and Fe. Further, as the composite metal oxide in which these elements are used as the element X, the element Y1, and the element Y2, a composite metal oxide containing Zr as the element X, Ce as the element Y1, and W, Fe, or Mn as the element Y2 can be exemplified. In this example, the oxide of the element Y2 cracks the upgraded oil, and the oxide of the element X cracks water, and the oxide of the element , -. Y1 suppresses the degradation of the catalyst.
[0027]
In the composite metal oxide containing the element X, the element Y1, and the element Y2, it is particularly preferred that the element X is zirconium (Zr) . It is because if Zr is used as the element X, even in the case where the catalyst is used under high-temperature and high-pressure conditions, the structure of the composite metal oxide can be maintained. That is, in the case of the composite metal oxide (cracking catalyst) containing Zr as the element X, the following problem does not occur: the crystal structure of the catalyst is largely changed by high-temperature and high-pressure steam so that the catalyst cannot be used as in the case of a hydrogenation catalyst containing hydrothermally synthesized zeolite, silica, or y-alumina to be used for hydrogenation cracking of a hydrocarbon oil. Further, the degradation of the catalyst hardly occurs, and also there is no need to perform a pretreatment (desulfurization or denitrogenation) of the hydrocarbon oil. Incidentally, from the viewpoint that the structure of the composite metal oxide is reliably maintained, the molar ratio (x/m) of the abundance x of the element X to the abundance m of all the metal elements in the catalyst is preferably 0.55 or more, more preferably 0.60 or more.
[0028]
Incidentally, the above-described composite metal oxide ' can be prepared using a known method such as a coprecipitation method or a sol-gel method. Specifically, for example, in the case of using a coprecipitation method, there is no particular restriction, and for example, the composite metal oxide can be prepared as follows.
(i) First, an aqueous solution containing metal elements constituting the composite metal oxide is prepared.
(ii) Subsequently, to the thus prepared aqueous solution, a coprecipitation agent such as an aqueous ammonia solution or an aqueous sodium carbonate solution is added dropwise while adjusting the pH of the aqueous solution so as not to shift the pH toward the alkaline side (for example, so that the pH
falls within a range of 5 to 8), whereby a coprecipitate is produced.
(iii) Then, finally, the obtained precipitate is filtered and dried, and thereafter, the dried precipitate is calcined, whereby a composite metal oxide is obtained.
Here, the temperature at which the precipitate is dried in the above (iii) is preferably 100 C or higher from the viewpoint that water is efficiently evaporated, and is preferably 160 C or lower from the viewpoint that rapid drying is prevented. Further, the calcination temperature for the dried precipitate is preferably 500 C or higher from the viewpoint that the structural stability of the composite metal oxide (catalyst) to be produced is achieved (that is, the change , in the structure of the composite metal oxide when a hydrocarbon oil is cracked using this composite metal oxide as the catalyst is suppressed) , and is preferably 900 C or lower from the viewpoint that a decrease in the surface area of the composite metal oxide to be produced is suppressed.
[0029]
As another example of the cracking catalyst, a catalyst containing alumina and a metal composite oxide which does not contain the element Y1, but contains the following two elements:
Zr as the element X and Fe as the element Y2 may be used. As still another example of the cracking catalyst, a catalyst containing a metal oxide of Zr or Ti which is the element X
and alumina to be used for the hydrogenation cracking of a hydrocarbon oil can also be used.
[0030]
(Reaction conditions) The cracking step using the above-described cracking catalyst is performed under a temperature condition of, for example, 375 to 550 C, preferably a temperature condition of 390 to 500 C is selected. If the temperature is lower than 375 C, water is not in a supercritical state, and further, an activation energy necessary for the reaction cannot be obtained and therefore a sufficient amount of hydrogen may not be obtained. On the other hand, under a temperature condition exceeding 550 C, a more than necessary amount of hydrogen is =
generated, and also due to the progression of thermal cracking, the upgraded oil may be vaporized to reduce the liquid yield, or the generated hydrogen may be consumed again. Further, there is also a concern that the olefin or diene content is increased due to thermal cracking.
[0031]
Further, as the pressure condition in the cracking step, a pressure condition of 0.1 to 40 MPa is selected. If the pressure is less than 0.1 MPa, the reaction does not sufficiently proceed or it is difficult to allow the upgraded oil and water to smoothly flow in the cracking reactor 1 in some cases, and if the pressure exceeds 40 MPa, the production cost of the cracking reactor 1 may be increased.
[0032]
[Hydrogenation step]
(Reaction) In the hydrogenation step, the cracked hydrocarbon oil and hydrogen are brought into contact with a hydrogenation catalyst to hydrogenate the cracked hydrocarbon oil and cleave the double bond, whereby the olefin or diene content is reduced.
[0033]
(Hydrogenation catalyst) Here, in the cracking step upstream of the hydrogenation step, the cracked hydrocarbon oil and hydrogen are produced using water, and therefore, water is contained in the cracked . CA 02883104 2015-02-25 =
. hydrocarbon oil in some cases. Accordingly, it is preferred to use, as the hydrogenation catalyst for allowing the above-described hydrogenation reaction to proceed, a catalyst in which a metal having a hydrogenation activity is carried on a support composed of a metal oxide which does not include alumina (particularly y-alumina) or silica causing a large change in the crystal structure of the catalyst due to high-temperature and high-pressure steam so that the catalyst cannot be used.
[0034]
As the metal oxide serving as the support which is hardly degraded by steam, for example, zirconia or anatase-type titanium dioxide (Ti02), or a mixture containing such zirconia and anatase-type titanium dioxide can be exemplified. The crystal structure of anatase-type titanium dioxide can be evaluated using, for example, an X-ray diffraction analysis.
In the case of anatase-type titanium dioxide, a diffraction peak (20 = 25.5 ) corresponding to a (101) plane appears in the X-ray diffraction spectrum.
[0035]
As the metal (active metal) having a hydrogenation activity to be carried on the above-described support, at least one metal selected from the group consisting of nickel, cobalt, and molybdenum can be selected.
Incidentally, from the viewpoint that the hydrogenation performance is sufficiently ' , ensured, the total amount of zirconia or anatase-type titanium dioxide to be mixed in the mixture constituting the support of the hydrogenation catalyst is preferably 50% by mass or more, more preferably 55% by mass or more, particularly preferably 60% by mass or more with respect to the amount of the mixture.
In the case where a step of removing water in the cracked hydrocarbon oil is provided between the cracking step and the hydrogenation step so that the water content in the hydrocarbon oil can be reduced, a hydrogenation catalyst in which the active metal is carried on a support including y-alumina or silica as the support may be used.
[0036]
(Reaction condition) The hydrogenation step using the above-described hydrogenation catalyst is performed under a temperature condition of, for example, 100 to 374 C, preferably a temperature condition of 200 to 350 C is selected. If the temperature is lower than 100 C, an activation energy necessary for the reaction cannot be obtained and therefore the olefin or diene content may not be able to be sufficiently reduced.
On the other hand, under a temperature condition exceeding 374 C, the hydrogenation reaction and the thermal cracking may proceed simultaneously, and therefore, the cracked hydrocarbon oil may be vaporized to reduce the liquid yield.
[0037]

Further, as for the pressure condition in the hydrogenation step, as the upper limit of the pressure, a pressure equivalent to that in the former part of the cracking step is selected, and as the lower limit of the pressure, a pressure condition of 0.5 MPa is selected, and as a more preferred range, a range of 1 to 5 MPa is selected. If the pressure is less than 0.5 MPa, the reaction does not sufficiently proceed or it is difficult to allow the cracked hydrocarbon oil and hydrogen to smoothly flow in the hydrogenation reactor 2 in some cases. On the other hand, in the case where the hydrogenation step is performed at a pressure exceeding the pressure in the cracking step, a pressure rising operation or the like is required, and therefore, such a case is not preferred. In addition, an undesirable reaction, for example, a reaction in which nuclear hydrogenation of an aromatic hydrocarbon in the hydrocarbon oil proceeds to excessively consume hydrogen and coke is deposited may proceed.
Further, the production cost of the hydrogenation reactor 2 may be increased.
[0038]
Here, the above-described reaction conditions are set so as to satisfy the target values previously determined in consideration of, for example, the transportability or the like of a heavy hydrocarbon oil such as a synthetic crude oil. As described previously, in Canada, the olefin concentration is - defined to be 1% or less in the specification of the pipeline, however, this value varies depending on the characteristics of the raw oil, weather conditions of the region where the synthetic crude oil is transported, and so on, and therefore, it is difficult to determine a uniform value applicable in all cases.
[0039]
On the other hand, in the case where the hydrogenation reaction is allowed to excessively proceed, the nuclear hydrogenation of an aromatic hydrocarbon in the hydrocarbon oil proceeds, and therefore hydrogen is excessively consumed, or coke is liable to be deposited on the surface of the catalyst, and therefore, the catalyst may be inactivated, and therefore, such a case is not desirable. Further, the amount of generated gas may be increased to decrease the liquid yield, and therefore, the necessity of reducing the olefin or diene content to a value lower than the above-described target value is low. In addition, if the progression of the hydrogenation reaction is confined to such an extent that the above-described transportability can be ensured, the consumption of hydrogen can be reduced, and further, a decrease in liquid yield in also the cracking step is suppressed, and thus, it is also possible to reduce the size of the cracking reactor 1.
[0040]
A double bond located at a terminal of the carbon backbone or a side chain has higher reactivity than a double bond located on the inside of the terminal. Therefore, it is considered that by hydrogenating the terminal double bond, a polymerization reaction of an olefin or a diene can be largely decreased.
Here, by focusing on the molecular structure of an olefin or a diene, a double bond located at a terminal of the carbon backbone or a side chain can allow the hydrogenation reaction to proceed under milder conditions (low temperature, low pressure, and low hydrogen/oil ratio) as compared with a double bond located on the inside of the terminal. Therefore, if the hydrogenation reaction can be allowed to proceed under conditions as mild as possible while meeting the previously set target value by adjusting the conditions for the hydrogenation reaction in light of this molecular structure, it is also possible to find the reaction conditions capable of suppressing the generation of gas so as to achieve a high liquid yield.
[0041]
In view of this, by focusing on the position of the double bond in the cracked hydrocarbon after the hydrogenation reaction, an index which indicates that a double bond on the terminal side is reduced than on the internal side is set, and the reaction conditions for the hydrogenation reaction may be set so as to meet this index. As such an index, when the ratio = of the amount of hydrogen bonded to a double bond located at a terminal position of a diene or an olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by A and the ratio of the amount of hydrogen bonded to a double bond located on the inside of the terminal position to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by B, the value of A/B can be exemplified.
Incidentally, the ratio of the amount of hydrogen can be determined by 1H-NMR.
[0042]
For example, the reaction conditions are set such that the value of A/B falls within a range of 0 to 0.5, preferably a range of 0 to 0.3. As shown in the Examples described below, if the value of A/B exceeds 0.5, the olefin or diene content may not be able to be sufficiently reduced.
[0043]
[Processing apparatus]
Next, a structural example of a processing apparatus according to an embodiment will be described with reference to Figs. 2 to 5. Incidentally, common reference numerals are used for common units in the respective processing apparatuses in these drawings.
Fig. 2 corresponds to the schematic flow shown in Fig.
1(a) and shows an apparatus for processing a hydrocarbon oil =
- provided attached to a upgrading process 3 which uses water when performing a upgrading processing. In this example, a mixed fluid of a upgraded oil and water flowing out of the upgrading process 3 is supplied to a cracking reactor 1 through a pump 11 and a heating unit 12, and brought into contact with a cracking catalyst, whereby a cracked hydrocarbon oil and hydrogen are produced.
[0044]
After the mixed fluid containing these cracked hydrocarbon oil and hydrogen is cooled in a cooling unit 13, free water is separated by an oil-water separator 14. Water collected in a boot of the oil-water separator 14 is discharged through a cooling unit 15 and a flow rate regulator valve 16, and reused in, for example, the upgrading process 3. The oil-water separation performed by the oil-water separator 14 corresponds to a step of separating water from a mixture of the cracked hydrocarbon oil and hydrogen (an oil-water separating step). The provision of the oil-water separating step (the oil-water separator 14) may be omitted as needed.
[0045]
The mixed fluid of the cracked hydrocarbon and hydrogen from which free water has been separated by the oil-water separator 14 is supplied to a hydrogenation reactor 2 through a cooling unit 21 and a pressure regulator valve 22, and comes into contact with a hydrogenation catalyst, whereby the olefin = or diene content is reduced. Thereafter, a mixed fluid containing the cracked hydrocarbon, gas generated by the hydrogenation reaction, surplus hydrogen, etc. flows in an oil-water separator 25 through a cooling unit 23 and a pressure regulator valve 24. Then, the cracked hydrocarbon separated from free water and gas is shipped out as a synthetic crude oil having a reduced olefin or diene content.
[0046]
Fig. 3 corresponds to the schematic flow shown in Fig.
1(b) and shows an apparatus for processing a cracked hydrocarbon oil provided attached to a upgrading process 3 which does not use water when performing a upgrading processing.
In this example, water is mixed in the upgraded oil flowing out of the upgrading process 3 through a pump 17 and a heating unit 18, which is a different point from the processing apparatus shown in Fig. 2.
[0047]
Next, in Fig. 4, a case in which the upgraded oil flowing out of the upgrading process 3 is subjected to fractional distillation in a distillation apparatus, and a fraction after the fractional distillation is processed in a cracking step is shown. In the example shown in Fig. 4, a mixed fluid of a upgraded oil and water flowing out of the upgrading process 3 and passing through a heating unit 41 is subjected to fractional distillation in a distillation column 42 and =
= fractionated into a light fraction and a heavy fraction, and then, a mixed fluid of the light fraction and water is processed in a cracking reactor 1. As described previously, a fraction having a distillation temperature of 60 to 220 C has a relatively high olefin or diene content, and therefore, the load applied to the cracking reactor 1 can be reduced by separating a heavy fraction having a low olefin or diene content and sending the residual fraction to the cracking step.
[0048]
Here, the use of the distillation column 42 is not limited to the case where the upgraded oil is separated into the following two fractions: a light fraction and a heavy fraction.
For example, in the case where an intermediate fraction has a high olefin or diene content, the upgraded oil is separated into the following three fractions: a light fraction, an intermediate fraction, and a heavy fraction, and the intermediate fraction may be processed in the cracking step.
Further, in the distillation apparatus shown in Fig. 4, a cooling unit and the like are provided on the top side of the distillation column 42, however, the description thereof is omitted here.
[0049]
Fig. 5 shows an example in which the processing apparatus according to this embodiment is provided attached to a supercritical water upgrading apparatus (see, for example, Japanese Patent Application Laid-Open Publication No.
=
2011-88964) with which a upgraded oil is thermally cracked using supercritical water as one example of the upgrading process 3.
A raw oil such as an extra-heavy crude oil is supplied to a supercritical water processing reactor 301 through a pump 302 and a heating unit 303 at such a temperature that polycondensation does not take place, for example, at 300 to 450 C. On the other hand, water is supplied to the supercritical water processing reactor 301 through a pump 304 and a heating unit 305 at a temperature not lower than the supercritical temperature (374 C), for example, at 450 to 600 C.
[0050]
In the supercritical water processing reactor 301, the pressure is 22.1 MPa (the critical pressure of water) or more, for example, from 25 to 30 MPa, and the temperature is from 374 to 500 C, and the thermal cracking of a raw oil proceeds in the inside of the supercritical water processing reactor 301. The thus obtained light oil component is extracted in the supercritical water phase and supplied to the cracking reactor 1. Then, the light oil component is subjected to the cracking step and the hydrogenation step, whereby a cracked hydrocarbon oil having a reduced olefin or diene content is obtained and used as a raw material of a synthetic crude oil, = CA 02883104 2015-02-25 -which is the same as in the case shown in Fig. 2. Further, water separated in each step is recycled again as a raw material of supercritical water through a recycled water tank 56 or a line provided with a pump 57 or 19. The cracking step may be performed by placing the cracking catalyst in the inside of the supercritical water processing reactor 301 without providing the cracking reactor 1.
[0051]
On the other hand, the heavy oil component which is not extracted in supercritical water is supplied to a flash drum 53 at a pressure condition of about 0.1 to 8 MPa and a temperature condition of about 250 to 430 C through a cooling unit 51 and a flow rate regulator valve 52, and water and a light oil component dissolved in the heavy oil component are separated by flash distillation. The water and the light oil component separated by flash distillation are separated from each other through a cooling unit 54 and an oil-water separator 55, and the light oil component is used as a raw material of a synthetic crude oil, and the water is recycled. Here, the light oil component may be processed in the cracking step and the hydrogenation step to reduce the olefin or diene content.
A part of the heavy oil component separated from the light oil component and the like in the flash drum 53 is mixed in a synthetic crude oil, and the residue serving as a residual oil is used as fuel or the like for a heating furnace serving as a heating unit 303 or 305.
[0052]
According to this embodiment, the following advantageous effect is exhibited. By using hydrogen produced by bringing water and a hydrocarbon oil containing a diene or an olefin (for example, a upgraded oil processed by the upgrading process 3) into contact with a cracking catalyst, a hydrogenation reaction of a cracked hydrocarbon oil obtained along with this hydrogen is performed, and therefore, even in a situation where it is difficult to obtain hydrogen, a cracked hydrocarbon oil having a reduced diene or olefin content can be obtained.
[0053]
Here, in the above-described example, by focusing on the reduction of an olefin or a diene which is problematic when transporting a synthetic crude oil or the like, a case where a upgraded oil flowing out of a upgrading process provided at a well site is processed in a cracking step and a hydrogenation step is exemplified. However, the application of the invention to a upgraded oil obtained from a upgrading process provided in an oil refinery or the like as needed is not excluded.
[Examples]
[0054]
[Characteristics of upgraded oil]
The characteristics of a upgraded oil used in an . CA 02883104 2015-02-25 =
= experiment described below are shown in Table 1. The quantitative determination of the ratio of the amount of hydrogen attributed to olefins (total olefin H) in a hydrocarbon oil to the total amount of hydrogen in the hydrocarbon oil was performed by a proton NMR analysis (NMR
system-500, manufactured by Varian, Inc.). Here, among the total olefin H, hydrogen bonded to carbon located at a terminal end of the carbon backbone or a side chain (terminal olefin H) and hydrogen bonded to carbon located on the inside of the carbon located at the terminal end (internal olefin H) are distinguished from each other on the basis of the positions of the NMR peaks.
In Table 1, CGO+LCO denotes a mixed oil of a cracked light oil (Coker Gas Oil: CGO) obtained from a coker and LCO (Light Cycle Oil) obtained from FCC. Further, a supercritical water upgraded oil denotes a upgraded oil (corresponding to a light oil component and containing water) obtained by upgrading using a supercritical water processing process exemplified in the supercritical water processing reactor 301 shown in Fig. 5.

' [Table 1]
CGO+LCO Supercritical water upgraded oil Specific gravity g/cc 0.910 0.922 Elementary S (X-ray fluorescence) wt% 0.71 3.26 analysis N (vacuum method) wt% 0.061 0.149 Lower than 180 C wt% 5.0 7.0 180-270 C wt% 52.5 19.0 Distillation 270-360 C wt% 41.0 33.0 characteristics 360-540 C wt% 1.5 37.0 Higher than 540 C wt% 0.0 4.0 Diene value 0.82 4.74 Results of proton NMR
aromatic hydrogen %H 16.4 5.4 H at allylic position %H 23.2 14.3 Paraffin H %H 53.2 65.3 Naphthene H %H 6.4 14.0 Total olefin H %H 0.7 tO
Terminal olefin H %H 0.39 0.51 Internal olefin H %H 0.36 0.47 [0055]
(Experiment 1) An examination was made as to how much the total olefin H in a upgraded oil was reduced by the hydrogenation step.
A. Experimental conditions A upgraded oil having characteristics shown in Table 2 was processed in the cracking step and the hydrogenation step, and a change in total olefin H was examined.
(Example 1-1) Processing was performed for CGO+LCO using a test apparatus having the same structure as that of the processing apparatus shown in Fig. 3. As the cracking catalyst in the cracking reactor 1, a composite metal oxide containing Zr as , . the element X, Ce as the element Y1, and W as the element Y2, and having a value of x/(171+Y2) of 1 and a value of y2/yl of 0.06 was used. Further, as the hydrogenation catalyst in the hydrogenation reactor 2, a catalyst in which Ni-Mo as active metals were carried on a support composed of 100% by mass of anatase-type titanium dioxide was used.
(Example 1-2) Processing was performed for upgraded oil obtained from a supercritical water upgrading apparatus having the same structure as that of the processing apparatus shown in Fig.
2. The structures of the cracking catalyst and the hydrogenation catalyst are the same as those in Example 1-1 (the conditions for the catalysts are the same in the following respective Examples).
[Table 2]
CGO+LCO Supercritical water upgradedoil Total olefin H %H 0.74 0.98 Terminal olefin H %H 0.39 0.51 Internal olefin H %H 0.36 0.47 <Reaction conditions>
Feedstock oil flow rate: 50 ml/hr (a) Cracking reaction Temperature: 430 C, Pressure: 25 MPaG, water/oil ratio:
1.58 (weight ratio) (b) Hydrogenation reaction Temperature: 100, 150, 200, 250, 300, and 350 C, -=
- Pressure: 5 MPaG
[0056]
B. Experimental Results A graph in which the horizontal axis represents the temperature of the hydrogenation reaction and the longitudinal axis represents the ratio [%H] of the total olefin H to the total hydrogen amount in the oil after the reaction is shown in Fig. 6. Here, the total olefin H was calculated by adding the ratios of the amounts of hydrogen attributed to the terminal olefin and the internal olefin, respectively. Further, the fine dashed line indicates the total olefin H in CGO+LCO before hydrogenation as a base line, and the bald dashed line indicates the total olefin H in the upgraded oil obtained from supercritical water upgrading before hydrogenation as a base line. In both the cases of Example 1-1 (CGO+LCO) and Example 1-2 (supercritical water upgraded oil) , as the hydrogenation temperature was increased, the total olefin H was decreased.
It is found that the content of olefin H was reduced by the hydrogenation step.
[0057]
(Experiment 2) CGO+LCO was subjected to the cracking step and the hydrogenation step, and a change in ratio of the terminal olefin H or the internal olefin H was examined.
A. Experimental conditions . (Example 2) =
Processing was performed using the same CGO+LCO and test apparatus as in Example 1-1.
<Reaction conditions>
Feedstock oil flow rate: 50 ml/hr (a) Cracking reaction Temperature: 430 C, Pressure: 25 MPaG, water/oil ratio:
1.58 (weight ratio) (b) Hydrogenation reaction Temperature: 100, 150, 200, 250, 300, and 350 C, Pressure: 5 MPaG
[0058]
B. Experimental results The ratio [%H] of the terminal olefin H or the internal olefin H to the total hydrogen amount in the cracked hydrocarbon oil after performing the cracking step and the hydrogenation step of CGO+LCO (hereinafter referred to as produced oil for the sake of convenience) is shown in Fig. 7. In Fig. 7, the horizontal axis represents the temperature of the hydrogenation reaction and the longitudinal axis represents the ratio of the terminal or internal olefin H. In the drawing, the terminal olefin H (corresponding to the "hydrogen amount ratio A" in the scope of claims) is plotted with lozenges, and the internal olefin H (corresponding to the "hydrogen amount ratio B" in the scope of claims) is plotted with triangles.

, ' .
Further, the fine dashed line in the drawing indicates the terminal olefin H in CGO+LCO before upgrading as a base line, and the bald dashed line indicates the internal olefin H in the same oil before upgrading as a base line (the same shall apply to Figs. 9, 10, and 12 with respect to the horizontal axis, the longitudinal axis, and the legends).
Further, from the obtained ratio of the terminal olefin H and the ratio of the internal olefin H, the ratio of the terminal olefin H to the internal olefin H (corresponding to the value of "A/B" in the scope of claims) was calculated, and a graph in which the obtained values are plotted against the temperature of the hydrogenation reaction is shown in Fig. 8.
In Fig. 8, the horizontal axis represents the temperature of the hydrogenation reaction, and the longitudinal axis represents the value of the ratio of the terminal olefin H to the internal olefin H (the same shall apply to Fig. 11 with respect to the horizontal axis and the longitudinal axis).
[0059]
According to Fig. 7, under the low-temperature conditions between 100 and 200 C, as the temperature of the hydrogenation reaction was increased, the terminal olefin H
was rapidly decreased, but the internal olefin H was not decreased. Further, under the conditions of 200 C or lower, the ratio of the internal olefin H was higher than that in CGO+LCO used as the raw material. This is considered to be = CA 02883104 2015-02-25 because a part of the terminal olefin H was translocated and became internal olefin H so that the ratio of the internal olefin H was increased as compared with that in the raw material.
Further, when extrapolating the results shown in Fig. 7, it is presumed that under the conditions of a temperature lower than 100 C, either of the terminal olefin and the internal olefin is hardly hydrogenated.
[0060]
Under the conditions in which the temperature of the hydrogenation reaction was from 250 to 350 C, as the temperature was increased, both of the terminal olefin H and the internal olefin H were decreased. On the other hand, when the temperature is increased to a high temperature exceeding 350 C, it is predicted that a problem arises that nuclear hydrogenation of an aromatic ring occurs to increase the consumption of hydrogen, or a hydrocarbon having a low boiling point such as methane is generated to decrease the yield of the liquid.
[0061]
Next, when a change in the value of the ratio of the terminal olefin H to the internal olefin H shown in Fig. 8 was examined, under the low temperature conditions in which the temperature of the hydrogenation reaction was between 100 and 200 C, as the temperature was increased, the value of the ratio of the terminal olefin H to the internal olefin H was rapidly = decreased. This is because the transition of the internal -olefin H was substantially constant, but the terminal olefin H was drastically decreased as the temperature was increased.
It is shown that under such temperature conditions, the internal olefin is hardly hydrogenated, but the terminal olefin is hydrogenated.
[0062]
On the other hand, there was a tendency that the value of the ratio of the terminal olefin H to the internal olefin H was decreased as the temperature was increased also under the temperature conditions between 250 and 350 C, but the decreasing degree was small. It is considered that at the same time as the terminal olefin was hydrogenated, the internal olefin was also hydrogenated, and therefore, the decreasing degree was small. On the other hand, the reason why a decreasing tendency in the value was still observed is considered to be because the decrease in the internal olefin was slower than the decrease in the terminal olefin.
[0063]
From the results shown in Fig. 8, it was found that the terminal olefin is more easily hydrogenated than the internal olefin. On the other hand, from the results shown in Fig. 7, it is presumed that the hydrogenation of the terminal olefin hardly occurs under the conditions of a temperature lower than 100 C, and therefore, it can be said that when the value of . CA 02883104 2015-02-25 - the ratio of the terminal olefin H to the internal olefin H
-is 0.5 or more, the terminal olefin is not sufficiently hydrogenated.
[0064]
(Experiment 3) A supercritical water upgraded oil was subjected to the cracking step and the hydrogenation step, and a change in ratio of the terminal olefin H or the internal olefin H was examined.
A. Experimental conditions (Example 3) The same supercritical water upgraded oil as in Example 1-2 was used. Further, in the test apparatus used for the processing of the supercritical water upgraded oil, the cooling unit 13 and the oil-water separator 14 in the latter part of the cracking reactor 1 were not provided, which is different from the processing apparatus shown in Fig. 2.
<Reaction conditions>
Feedstock oil flow rate: 50 ml/hr (a) Water cracking reaction Temperature: 430 C, Pressure: 25 MPaG, water/oil ratio:
1.58 (weight ratio) (b) Hydrogenation reaction Temperature: 200, 250, and 300 C, Pressure: 5 MPaG
[0065]
B. Experimental results = The ratio [%H] of the terminal olefin H or the internal olefin H to the total hydrogen amount in the produced oil after performing the cracking step and the hydrogenation step of the supercritical water upgraded oil is shown in Fig. 9.
According to Fig. 9, in a temperature range of 200 to 300 C, the ratio of the terminal olefin H was sufficiently decreased, and it was confirmed that even in the case where the oil-water separation step was not provided before the hydrogenation step, the content of the olefin H could be reduced.
[0066]
(Experiment 4) A supercritical water upgraded oil was subjected to the cracking step and the hydrogenation step, and a change in ratio of the terminal olefin H or the internal olefin H was examined.
A. Experimental conditions (Example 4) Processing was performed using the same supercritical water upgraded oil and test apparatus as in Example 1-2.
<Reaction conditions>
Feedstock oil flow rate: 50 ml/hr (a) Cracking reaction Temperature: 430 C, Pressure: 25 MPaG, water/oil ratio:
1.58 (weight ratio) (b) Hydrogenation reaction , ' = Temperature: 100, 150, 200, 250, 300, and 350 C, Pressure: 5 MPaG
[0067]
B. Experimental results The ratio [96H] of the terminal olefin H or the internal olefin H to the total hydrogen amount in the produced oil after performing the cracking step and the hydrogenation step of the supercritical water upgraded oil is shown in Fig. 10, and a change in the ratio of the terminal olefin H to the internal olefin H is shown in Fig. 11.
According to Fig. 10, almost the same tendency was observed with respect to the change in the ratio of the terminal olefin H or the internal olefin H against the temperature of the hydrogenation reaction as in the case of Example 2 shown in Fig. 7 (the case where the same processing was performed for CGO+LCO). Further, also with respect to the ratio of the terminal olefin H to the internal olefin H, the same tendency was observed as in Example 2 shown in Fig. 8.
[0068]
(Experiment 5) A light fraction (a fraction lighter than a light oil (distillation characteristics: 360 C or lower)) obtained by distilling the supercritical water upgraded oil by a distillation apparatus was subjected to the cracking step and the hydrogenation step, and a change in ratio of the terminal =
- olefin H or the internal olefin H was examined.
A. Experimental conditions (Example 5) Processing was performed using the same supercritical water upgraded oil as in Example 1-2, and also using a test apparatus having the same structure as that of the processing apparatus shown in Fig. 4.
The ratio of the terminal olefin H or the internal olefin H contained in the light fraction is shown in Table 3.
[Table 3]
Terminal olefin H %H 0.94 Internal olefin H %H 0.87 <Reaction conditions>
Feedstock oil flow rate: 50 ml/hr (a) Cracking reaction Temperature: 430 C, Pressure: 25 MPaG, water/oil ratio:
1.58 (weight ratio) (b) Hydrogenation reaction Temperature: 200, 250, and 300 C, Pressure: 5 MPaG
[0069]
B. Experimental results The ratio [%H] of the terminal olefin H or the internal olefin H to the total hydrogen amount in the produced oil after performing the cracking step and the hydrogenation step of the light fraction obtained by distilling the supercritical water upgraded oil is shown in Fig. 12.

' . According to Fig. 12, it was confirmed that also when the light fraction obtained by distilling the supercritical water upgraded oil was used as a raw material, the content of olefin H was decreased. It becomes possible to increase a feedstock oil which can be processed by the upgrading process and to reduce the amount of a catalyst used by subjecting a part of the fraction obtained by performing distillation after the upgrading process to the cracking step and the hydrogenation step.
The tendency observed in the above-described Examples is also applicable to the case where the combination of the elements X, Y1, and Y2 of the cracking catalyst, the value of x/(y1d-Y2) or y2/y1, the content ratio of titanium dioxide in the hydrogenation catalyst, the type of active metal, or the like is changed. Therefore, the technical scope of the invention is not limited only to the case where the cracking catalyst and the hydrogenation catalyst used in the above-described Examples are used.
[Reference Sings List]
[0070]
1: cracking reactor 14: oil-water separator 2: hydrogenation reactor 3: upgrading process 301: supercritical water processing reactor 42: distillation column

Claims

[Claim 1]
A method for processing a hydrocarbon oil, characterized by comprising:
a step of producing a cracked hydrocarbon oil and hydrogen by bringing water and a hydrocarbon oil containing at least one of a diene and an olefin into contact with a cracking catalyst at a temperature of 375 to 550°C to effect cracking;
and a step of reducing the content of at least one of the diene and the olefin by bringing the hydrogen and the cracked hydrocarbon oil into contact with a hydrogenation catalyst at a temperature of 100 to 374°C to effect a hydrogenation reaction of the cracked hydrocarbon oil.
[Claim 2]
The method for processing a hydrocarbon oil according to claim 1, characterized in that the method further comprises a step of separating water from a mixture containing the cracked hydrocarbon oil and water after the contact with the cracking catalyst, and the hydrogenation reaction is performed for the cracked hydrocarbon oil after separating water.
[Claim 3]
The method for processing a hydrocarbon oil according to claim 1 or 2, characterized in that the hydrocarbon oil contains a upgraded oil obtained by upgrading of feedstock oil with water, and water to be used for producing hydrogen by the cracking catalyst is water discharged along with the upgraded oil.
[Claim 4]
The method for processing a hydrocarbon oil according to any one of claims 1 to 3, characterized in that the hydrocarbon oil contains a upgraded oil obtained by bringing a feedstock oil into contact with supercritical water.
[Claim 5]
The method for processing a hydrocarbon oil according to claim 3 or 4, characterized in that the hydrocarbon oil contains at least one fraction obtained by separating the upgraded oil into a plurality of fractions having different boiling point ranges through distillation.
[Claim 6]
The method for processing a hydrocarbon oil according to any one of claims 1 to 5, characterized in that the hydrogenation reaction is performed such that when the ratio of the amount of hydrogen bonded to a terminal carbon-carbon double bond of the diene or the olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by A and the ratio of the amount of hydrogen bonded to an internal carbon-carbon double bond of the diene or the olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by B, the value of A/B falls within a range of 0 to 0.5.
[Claim 7]
The method for processing a hydrocarbon oil according to any one of claims 1 to 6, characterized in that the cracking catalyst is a composite metal oxide, which contains:
(a) one element X selected from Group IVA elements;
(b) one element Y1 selected from the group consisting of Group IIIA elements, Group VIA elements , Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y1 is an element different from the element X); and (c) one element Y2 selected from the group consisting of Group IIIA elements , Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y2 is an element different from the element X and the element Y1), and in which (d) the ratio of the abundance x of the element X to the sum (y1+y2) of the abundance y1 of the element Y1 and the abundance y2 of the element Y2 is 0.5 or more and 2.0 or less, and (e) the ratio of the abundance y2 of the element Y2 to the abundance y1 of the element Y1 is 0.02 or more and 0.25 or less.
[Claim 8]
The method for processing a hydrocarbon oil according to claim 7, characterized in that the element X is Zr, the element Y1 is Ce, and the element Y2 is an element selected from a Y2 element group consisting of W, Fe, and Mn.
[Claim 9]
The method for processing a hydrocarbon oil according to any one of claims 1 to 8, characterized in that the hydrogenation catalyst is configured such that a metal having a hydrogenation activity is carried on a support composed of a metal oxide which does not include alumina or silica.
[Claim 10]
The method for processing a hydrocarbon oil according to claim 9, characterized in that the hydrogenation catalyst is configured such that at least one metal selected from the group consisting of nickel, cobalt, and molybdenum is carried on a support containing zirconia or anatase-type titania.
[Claim 11]
An apparatus for processing a hydrocarbon oil, characterized by comprising:
a cracking reactor, which is supplied with water and a hydrocarbon oil containing at least one of a diene and an olefin, and is packed with a cracking catalyst which produces a cracked hydrocarbon oil and hydrogen from the hydrocarbon oil and the water; and a hydrogenation reactor, which is supplied with the hydrogen produced in the cracking reactor and the cracked hydrocarbon oil flowing out of the cracking reactor, and is packed with a hydrogenation catalyst which reduces the content of at least one of the diene and the olefin by allowing a hydrogenation reaction of the cracked hydrocarbon oil to proceed.
[Claim 12]
The apparatus for processing a hydrocarbon oil according to claim 11, characterized in that the apparatus further comprises an oil-water separator tank which separates water from a mixture containing water and the cracked hydrocarbon oil flowing out of the cracking reactor, and to the hydrogenation reactor, the cracked hydrocarbon oil after separating water in the oil-water separator tank is supplied.
[Claim 13]
The apparatus for processing a hydrocarbon oil according to claim 11 or 12, characterized in that the hydrocarbon oil contains a upgraded oil obtained from a upgrading apparatus which upgrades a feedstock oil using water, and water to be used for producing hydrogen by the cracking catalyst is water discharged along with the upgraded oil.
[Claim 14]
The apparatus for processing a hydrocarbon oil according to any one of claims 11 to 13, characterized in that the hydrocarbon oil contains a upgraded oil obtained from a supercritical water upgrading apparatus which upgrades a feedstock oil by bringing the feedstock oil into contact with supercritical water.
[Claim 15]
The apparatus for processing a hydrocarbon oil according to claim 13 or 14, characterized in that the hydrocarbon oil contains at least one fraction obtained from a distillation apparatus which separates the upgraded oil into a plurality of fractions having different boiling point ranges through distillation.
[Claim 16]
The apparatus for processing a hydrocarbon oil according to any one of claims 11 to 15, characterized in that the hydrogenation reaction is performed such that when the ratio of the amount of hydrogen bonded to a terminal carbon-carbon double bond of the diene or the olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by A and the ratio of the amount of hydrogen bonded to an internal carbon-carbon double bond of the diene or the olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is represented by B, the value of A/B falls within a range of 0 to 0.5.
[Claim 17]

The apparatus for processing a hydrocarbon oil according to any one of claims 11 to 16, characterized in that the cracking catalyst is a composite metal oxide, which contains:
(a) one element X selected from Group IVA elements;
(b) one element Y1 selected from the group consisting of Group IIIA elements, Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y1 is an element different from the element X) ; and (c) one element Y2 selected from the group consisting of Group IIIA elements, Group VIA elements, Group VIIA elements, Group IVA elements in the fourth to sixth periods, and Group VIII elements in the fourth period (provided that the element Y2 is an element different from the element X and the element Y1) , and in which (d) the ratio of the abundance x of the element X to the sum (y1+y2) of the abundance y1 of the element Y1 and the abundance y2 of the element Y2 is 0.5 or more and 2.0 or less, and (e) the ratio of the abundance y2 of the element Y2 to the abundance y1 of the element Y1 is 0.02 or more and 0.25 or less.
[Claim 18]
The apparatus for processing a hydrocarbon oil according to any one of claims 11 to 17, characterized in that the hydrogenation catalyst is configured such that a metal having a hydrogenation activity is carried on a support composed of a metal oxide which does not include alumina or silica.