RU2617846C2 - Method for hydrocarbon oil processing and plant for hydrocarbon oil processing - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method includes the step of cracked hydrocarbon oil and hydrogen production by bringing water and hydrocarbon oil containing at least one compound from diene and olefin, in contact with a cracking catalyst at a temperature of 375-550°C for cracking, and the step of reduction of content of at least one diene and olefin compound by bringing hydrogen and cracked hydrocarbon oil obtained in the previous step in contact with the hydrogenation catalyst at a temperature of 100-374° to provide hydrogenating of the cracked hydrocarbon oils. At that, the hydrogenation reaction is carried out in such a way, that, if the ratio of hydrogen content associated with a terminal double carbon-carbon bond of diene or olefin and hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is referred to as A, and the ration of hydrogen content associated with internal double carbon-carbon bond of diene or olefin and hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is referred to as B, the A/B value is in the range of 0 to 0.5.

EFFECT: reduction of olefins or dienes in a hydrocarbon oil.

16 cl, 12 dwg, 3 tbl, 6 ex

Description

Technical field

[0001]

The present invention relates to a method for reducing the content of olefin or diene in a hydrocarbon oil.

State of the art

[0002]

Although demand for crude oil in the future is expected to grow primarily in developing countries such as China and India, the extraction of light crude oil, which has been used traditionally, is nearing maximum, and therefore the need for heavy crude oil or superheavy oil is increasing crude oil, which in many respects has not yet been used. Among superheavy crude oils, in relation to Canadian oil sands bitumen and Orinoco Venezuelan bituminous oil, economical methods for their production have already been established and their production volumes are increasing.

[0003]

The density and viscosity of such superheavy crude oil is very high, and therefore, pre-treatment is necessary to transport it from the oil well in the producing region to the refinery in the consumer region using a pipeline or the like, without which superheavy crude oil cannot be transported. In this regard, the following two methods are selected at the well site: a dilution method in which a diluent is added to lower the viscosity; and a refinement method in which light synthetic crude oil is obtained by constructing a unit nearby called a refiner.

[0004]

However, the dilution method has the problem that the diluent, such as condensate, must be provided sufficiently, or that since the transported volume increases with the addition of the diluent, transport costs increase. In addition, also in the refinement method, the problem is that since a large-scale installation equivalent to that at a refinery is needed in a well section, it is economically justified only near a large oil field, another problem is the need to remove by-products such as coke and sulfur , or sometimes the problem of providing the hydrogen necessary for refining may arise.

[0005]

In light of these problems, the inventors of the present invention have developed a method for producing synthetic crude oil, which can be transported through a pipeline without resorting to a diluent, by refinement of heavy crude oil or superheavy crude oil using supercritical water in accordance with a simple scheme at the well site. However, the synthetic crude oil obtained here undergoes a series of heatings, wherein the hydrocarbons in the oil are cracked or the like, and therefore unsaturated hydrocarbons are formed, which leads to an increase in the concentration of olefin or diene. If the concentration of olefin or diene is high, the stability of the oil is low, and polymerization or the like occurs during transportation, and thus there is a risk of problems such as precipitation of the polymerized product in the pipeline or clogging of the pipeline with the polymerized product. Therefore, for example, in Canada, the concentration of olefins in pipeline specifications is limited to 1% or less. The content of such an olefin or diene can be reduced by a hydrogenation reaction, however, for this it is necessary to ensure the supply of hydrogen. In the case when there is no hydrogen production facility nearby, for example, at a well site, and it is difficult to produce hydrogen, it is usually necessary to construct a hydrogen production plant using natural gas or naphtha as a raw material. However, the construction of such a plant for producing hydrogen leads to an increase in construction costs, and also has the problem that it is difficult in some regions to produce natural gas or naphtha for use as a raw material, or the like.

[0006]

In a refinery, on the other hand, the cracking oil obtained from the FCC or coking unit has a relatively high concentration of olefins, and such olefins form a precipitate in the transport pipe or in the raffinate tank, and therefore can cause blockage or the like. . In this regard, sometimes it may be necessary to remove the olefin components in the cracking oil, however, when cleaning by hydrogenation in the traditional way, the problem is that the internal resources of hydrogen are consumed.

[0007]

PTL 1 - PTL 3 describes a method for converting a hydrocarbon oil to a light oil product in relation to a mixture of hydrocarbon oil and water, by carrying out a cracking reaction of a hydrocarbon oil in the presence of a catalyst or using water in a supercritical state (supercritical water), however, a method related with the processing of hydrocarbon oil containing olefin or diene.

List of links

Patent documents

[0008]

[PTL 1]: Japanese Patent Application Laid-Open No. 2008-297466, Claim 1, Paragraph [0017]

[PTL 2]: Japanese Patent Application Laid-Open No. 2009-242467, Claim 1, Paragraph [0028]

[PTL 3]: Japanese Patent Application Laid-Open No. 2006-7151, Claims 1, Paragraphs [0017], [0009] - [0010]

SUMMARY OF THE INVENTION

Technical challenge

[0009]

The present invention was developed taking into account the above circumstances, and the object of the present invention is to provide a method for processing hydrocarbon oil and a plant for processing hydrocarbon oil, by which the content of dienes or olefins in hydrocarbon oil can be reduced even when it is difficult to obtain hydrogen.

The solution of the problem

[0010]

A method of processing hydrocarbon oil in accordance with the invention is characterized in that it includes:

the step of producing cracked hydrocarbon oil and hydrogen by bringing water and a hydrocarbon oil containing at least one diene and olefin compound into contact with the cracking catalyst at a temperature of 375-550 ° C. to effect cracking; and

a step of reducing the content of at least one diene and olefin compound by bringing hydrogen and cracked hydrocarbon oil into contact with a hydrogenation catalyst at a temperature of 100-374 ° C. to carry out a hydrogenation reaction of cracked hydrocarbon oil.

[0011]

A hydrocarbon oil processing method may have the following characteristics.

(1) The method further includes the step of separating water from the mixture containing cracked hydrocarbon oil and water after contacting with the cracking catalyst, and a hydrogenation reaction is carried out for the cracked hydrocarbon oil after separation of the water.

(2) Hydrocarbon oil contains refined oil obtained by refining petroleum feedstock using water, and the water used to produce hydrogen using a cracking catalyst is water discharged along with refined oil. In addition, hydrocarbon oil contains refined oil obtained by bringing the crude oil into contact with supercritical water. Further, the hydrocarbon oil contains at least one fraction obtained by dividing the enriched oil into a number of fractions having different boiling temperature ranges by distillation.

(3) The hydrogenation reaction is carried out in such a way that if the ratio of the hydrogen content associated with the terminal carbon-carbon double bond of a diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is denoted as A and the ratio of the hydrogen content associated with the internal double carbon -carbon bond of a diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is denoted as B, then the A / B value is in the range from 0 to 0 ,5.

(4) The cracking catalyst is a mixed metal oxide, which contains:

(a) one element X selected from elements of group IVA;

(b) one element Y ₁ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₁ is an element other than element X); and

(c) one element Y ₂ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₂ is an element other than element X and element Y ₁ ); and in which

(d) the ratio of the content x of the element X to the sum (y ₁ + y ₂ ) of the content of ₁ element Y ₁ and the content of y _{2 of} element Y ₂ is 0.5 or more and 2.0 or less, and

(e) the ratio of the content of y ₂ element Y ₂ to the content of ₁ element Y ₁ is 0.02 or more and 0.25 or less.

For example, element X is Zr, element Y ₁ is Ce, and element Y ₂ is an element selected from the group of elements Y ₂ consisting of W, Fe and Mn.

(5) The hydrogenation catalyst is designed such that a metal having hydrogenation activity is supported on a support consisting of metal oxide, which does not include alumina or silica. For example, the hydrogenation catalyst is designed such that at least one metal selected from the group consisting of nickel, cobalt and molybdenum is supported on a carrier containing zirconia or anatase type titanium dioxide.

[0012]

Further, the installation for processing hydrocarbon oil in accordance with the invention is characterized by the inclusion of:

a cracking reactor that is supplied with water and a hydrocarbon oil containing at least one diene and olefin compound and loaded with a cracking catalyst that produces cracked hydrocarbon oil and hydrogen from hydrocarbon oil and water; and

a hydrogenation reactor, which is supplied with hydrogen obtained in the cracking reactor and cracked hydrocarbon oil flowing from the cracking reactor, and is loaded with a hydrogenation catalyst, which reduces the content of at least one compound from the number of diene and olefin, allowing the hydrogenation reaction of the cracked hydrocarbon oil.

[0013]

A hydrocarbon oil processing plant may have the following characteristics.

(6) The apparatus further includes an oil and water separation tank in which water is separated from a mixture containing water and cracked hydrocarbon oil discharged from the cracking reactor, and cracked hydrocarbon oil after separation of water in the oil and water separator is fed to the hydrogenation reactor.

(7) Hydrocarbon oil contains refined oil obtained from a refining unit that refines the crude oil using water, and the water used to produce hydrogen using a cracking catalyst is water discharged along with refined oil. In addition, the hydrocarbon oil contains refined oil obtained from a refining unit with supercritical water, which refines the petroleum feed by bringing the petroleum feed into contact with supercritical water. Further, the hydrocarbon oil contains at least one fraction obtained from a distillation unit, which separates the enriched oil into a number of fractions having different boiling temperature ranges by distillation.

(8) The hydrogenation reaction is carried out in such a way that if the ratio of the hydrogen content associated with the terminal carbon-carbon double bond of a diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is denoted as A and the ratio of the hydrogen content associated with the internal double carbon -carbon bond of a diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is denoted as B, then the A / B value is in the range from 0 to 0 ,5.

(9) The cracking catalyst is a mixed metal oxide, which contains:

(a) one element X selected from elements of group IVA;

(b) one element Y ₁ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₁ is an element other than element X); and

(c) one element Y ₂ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₂ is an element other than element X and element Y ₁ ); and in which

(d) the ratio of the content x of the element X to the sum (y ₁ + y ₂ ) of the content of ₁ element Y ₁ and the content of y _{2 of} element Y ₂ is 0.5 or more and 2.0 or less, and

(e) the ratio of the content of y ₂ element Y ₂ to the content of ₁ element Y ₁ is 0.02 or more and 0.25 or less.

(10) The hydrogenation catalyst is designed such that a metal having hydrogenation activity is supported on a support consisting of metal oxide, which does not include alumina or silica.

Beneficial effects of the invention

[0014]

In accordance with the invention, by using hydrogen obtained by bringing water and a hydrocarbon oil containing a diene or olefin into contact with a cracking catalyst, a hydrogenation reaction of the cracked hydrocarbon oil obtained with this hydrogen is carried out, and therefore, even in a situation when it is difficult to produce hydrogen, a cracked hydrocarbon oil with a reduced content of diene or olefin can be obtained. In addition, the amount of hydrogen produced can be adjusted according to the content of diene or olefin in the processed hydrocarbon oil.

Brief Description of the Drawings

[0015]

[FIG. 1] In FIG. 1 is an explanatory view showing a diagram of a method of the invention.

[FIG. 2] In FIG. 2 is a flowchart illustrating a first configuration example of a processing plant according to an embodiment of the invention.

[FIG. 3] In FIG. 3 is a flow diagram illustrating a second example of a processing plant configuration.

[FIG. 4] In FIG. 4 is a flowchart illustrating a third example of a processing plant configuration.

[FIG. 5] In FIG. 5 is a flowchart illustrating an example in which a refining unit is combined with a refining unit with supercritical water.

[FIG. 6] In FIG. 6 is a first explanatory view illustrating the results of an example.

[FIG. 7] In FIG. 7 is a second explanatory view illustrating the results of an example.

[FIG. 8] In FIG. 8 is a third explanatory view illustrating the results of an example.

[FIG. 9] In FIG. 9 is a fourth explanatory view illustrating the results of an example.

[FIG. 10] In FIG. 10 is a fifth explanatory view illustrating the results of an example.

[FIG. 11] In FIG. 11 is a sixth explanatory view illustrating the results of an example.

[FIG. 12] In FIG. 12 is a seventh explanatory view illustrating 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 compound of an olefin having a 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 an open chain hydrocarbon, a naphthenic hydrocarbon, or an aromatic hydrocarbon. In the case of an open chain hydrocarbon, the hydrocarbon may have a double bond in the main carbon chain or may have a double bond in the side chain. In the case of a naphthenic hydrocarbon or aromatic hydrocarbon, the double bond in the side chain associated with the naphthenic ring, aromatic ring or their fused ring is a target for processing. Such a hydrocarbon may contain, for example, oxygen, nitrogen or sulfur atoms. In this regard, in the invention, focusing on a hydrocarbon containing one or two double bonds and having a relatively low molecular weight, it is proposed to reduce the number of double bonds. However, it goes without saying that the content of double bonds in a hydrocarbon containing three or more double bonds can be reduced during the application of this processing.

[0017]

Olefin or diene is contained in a hydrocarbon oil undergoing a series of heatings, and this series of heatings is used in refining in a method or the like for converting a crude oil into a light oil product by removing or cracking a heavy oil component. Examples of a series of heating process include coking, FCC (fluid catalytic cracking), Eureka (registered trademark), in which thermal cracking of petroleum feeds is carried out in the presence of steam (water), CPJ, aqua conversion and supercritical water treatment, in which the light oil component obtained by bringing the heated oil feed into contact with supercritical water to effect thermal cracking is recovered into supercritical water.

[0018]

Examples of petroleum feedstocks for refining in this way include Middle Eastern heavy crude oils, heavy oils such as atmospheric distillation residues and heavy crude vacuum distillation residues, and superheavy crude oils such as Canadian oil sands bitumen and Orinoco Venezuelan bituminous oil. Here, hydrocarbon oil obtained by processing a petroleum feed using a refinement process, such as supercritical water treatment, is called refined oil.

[0019]

It is known that in a refined oil, for example, a fraction having a distillation temperature of 60-220 ° C has a relatively high olefin or diene content. The content of such an olefin or diene can be reduced by a hydrogenation reaction in which the carbon-carbon bond is cleaved, however, as described in the prior art, it is often difficult to obtain cheap hydrogen in the enrichment process provided for in the well site or the like.

In this regard, the inventors of the present invention have developed a method in which hydrogen is generated by a catalytic reaction of an upgraded oil using water, which can be easily obtained even at a well site or the like, and the olefin or diene content of the refined oil is reduced by a reaction hydrogenation using formed hydrogen.

[0020]

Method diagram

In FIG. 1 (a) and (b) shows a schematic flow diagram of a method in accordance with an embodiment. According to these illustrations, water and refined oil containing olefin or diene resulting from the refinement process 3 are supplied to the cracking reactor 1 and brought into contact with the cracking catalyst, resulting in the formation of cracked hydrocarbon oil and hydrogen (cracking step). These cracked hydrocarbon oil and hydrogen are fed to the hydrogenation reactor 2 and brought into contact with the hydrogenation catalyst to carry out the hydrogenation reaction, which reduces the olefin or diene content (hydrogenation step). A cracked hydrocarbon oil having a low olefin or diene content obtained from the hydrogenation reactor 2 can be used as a raw material for synthetic crude oil or the like.

The cracking reactor 1 is loaded with a cracking catalyst and the hydrogenation reactor 2 is loaded with a hydrogenation catalyst, however, the method of bringing the refined oil or cracked hydrocarbon oil into contact with each catalyst is not limited to the case in which such fluid passes through a fixed bed, and a favorable method can be applied, such as using a fluidized bed or fluidized bed plant.

[0021]

Here, as shown in FIG. 1 (a), in the refinement process 3 (for example, in the above process CPJ, Eureka, aqua conversion, supercritical water treatment, etc.), in which water is used in the treatment, the water supplied to the refinement process 3 for the refinement treatment , and then diverted from the refinement process 3 together with refined oil, can be used as water for the formation of hydrogen. On the other hand, in the case of a refining process 3 in which water is not used (for example, the coking described above, FCC, or the like), water is supplied to the cracking reactor 1 separately from the refined oil from the refining process 3 (Fig. 1 (b) )

[0022]

Cracking stage

(Reaction)

At the cracking stage, the refined oil and water are brought into contact with the cracking catalyst for cracking the refined oil and water, resulting in a cracked hydrocarbon oil and hydrogen. Regarding the cracking reaction of the fortified oil and water, for example, while the refined oil is cracked using oxygen in the oxide lattice contained in the cracking catalyst, the water is split by incorporating a water cleavage catalyst into the cracking catalyst, and the lattice defect is compensated by oxygen. Using this splitting of water, hydrogen is formed, and these cracked hydrocarbon and hydrogen are fed to the hydrogenation step.

[0023]

(Cracking catalyst)

As a cracking catalyst to enable the reaction described above to occur, for example, a mixed metal oxide, which is an oxide obtained by combining two or more metal oxides, can be used. In particular, a mixed metal oxide containing the indicated elements X, Y ₁ and Y ₂ can be used as a cracking catalyst. The crystal structure of the mixed metal oxide used as a cracking catalyst can be evaluated using, for example, X-ray diffraction analysis.

[0024]

An example of a mixed metal oxide containing said element X, said element Y ₁ and said element Y ₂ can be a mixed metal oxide containing the following three metal elements:

(a) one element X selected from elements of group IVA;

(b) one element Y ₁ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₁ is an element other than element X); and

(c) one element Y ₂ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₂ is element other than element X and element Y ₁ ) in the indicated relation.

[0025]

Here, as an example of the “specified ratio”, for example, the ratio (molar ratio) of the contents of the corresponding elements X, Y ₁ and Y ₂ in the catalyst, determined by the melting method / ICP-AES, can serve as follows:

(d) the ratio of the content x of the element X to the sum (y ₁ + y ₂ ) of the content of ₁ element Y ₁ and the content of y _{2 of} element Y ₂ is 0.5 or more and 2.0 or less (0.5≤x / ( y ₁ + y ₂ ) ≤2.0), and

(e) the ratio of the content of y _{2 of the} element Y ₂ to the content of _{1 of the} element Y ₁ is 0.02 or more and 0.25 or less (0.02≤y ₂ / y ₁ ≤0.25).

[0026]

Mixed metal oxide for use as a cracking catalyst is not limited to specific elements as long as it meets the requirements described above, however, specific examples of element X, element Y ₁ and element Y ₂ include Ti, Zr, Ce, W, Mn and Fe. In addition, an example of a mixed metal oxide in which these elements are used as element X, element Y ₁ and element Y ₂ can be a mixed metal oxide containing Zr as element X, Ce as element Y ₁ , and W, Fe or Mn as an element of Y ₂ . In this example, the oxide of element Y ₂ cracks the refined oil, and the oxide of element X breaks down water, and the oxide of element Y ₁ suppresses degradation of the catalyst.

[0027]

In a mixed metal oxide containing element X, element Y ₁ and element Y ₂ , it is particularly preferred that element X be zirconium (Zr). This is due to the fact that if Zr is used as element X, even when the catalyst is used under high temperature and high pressure conditions, the structure of the mixed metal oxide can be maintained. That is, in the case of using a mixed metal oxide (cracking catalyst) containing Zr as an element X, the following problem does not arise: the crystalline structure of the catalyst changes significantly under the influence of 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 γ-alumina, used for hydrocracking a hydrocarbon oil. In addition, there is almost no degradation of the catalyst, and there is also no need to pre-treat (desulfurize or de-nitrate) the hydrocarbon oil. In this regard, from the point of view that the structure of the mixed metal oxide is reliably maintained, the molar ratio (x / m) of the content x of the element X to the content m of all metal elements in the catalyst is preferably 0.55 or more, more preferably 0.60 or more.

[0028]

In this regard, the mixed metal oxide described above can be obtained using a known method, such as a coprecipitation method or a sol-gel method. In particular, for example, in the case of using the coprecipitation method, there are no particular restrictions, and, for example, a mixed metal oxide can be obtained as follows.

(i) First, an aqueous solution is obtained containing elements of metals forming a mixed metal oxide.

(ii) Then, a coprecipitation reagent, such as aqueous ammonia or aqueous sodium carbonate, is added dropwise to the aqueous solution thus obtained, adjusting the pH of the aqueous solution so as not to shift the pH to the alkaline side (for example, so that the pH value ranged from 5 to 8), resulting in a co-precipitation product.

(iii) Then, finally, the precipitate obtained is filtered off and dried, and then the dried precipitate is calcined, whereby a mixed metal oxide is obtained.

Here, the temperature at which the precipitate is dried in the above item (iii) is preferably 100 ° C or higher, in terms of the fact that the water evaporates efficiently, and preferably 160 ° C or lower, in terms of what is prevented quick drying. In addition, the calcination temperature for the dried precipitate is preferably 500 ° C. or higher in terms of achieving structural stability of the resulting mixed metal oxide (catalyst) (i.e., a change in the structure of the mixed metal oxide is suppressed by cracking a hydrocarbon oil using this mixed metal oxide as a catalyst), and preferably 900 ° C. or lower from the point of view of suppressing a decrease in the surface area of the resulting mixed metal oxide.

[0029]

As another example of a cracking catalyst, a catalyst containing alumina and mixed metal oxide, which does not contain the element Y ₁ but contains the following two elements: Zr as the element X and Fe as the element Y ₂ can also be used. As another example of a cracking catalyst, a catalyst comprising a metal oxide of Zr or Ti, which is an element X, and an aluminum oxide used for hydrocracking a hydrocarbon oil may also be used.

[0030]

(Reaction conditions)

The cracking step using the cracking catalyst described above is carried out under temperature conditions, for example, from 375 ° C. to 550 ° C. Preferably, temperature conditions from 390 ° C. to 500 ° C. are preferably selected. If the temperature is below 375 ° C, the water is not in a supercritical state, and in addition, the activation energy needed for the reaction cannot be obtained, and therefore, a sufficient amount of hydrogen cannot be obtained. On the other hand, at temperatures exceeding 550 ° C, more hydrogen is formed than necessary, and also due to the progression of thermal cracking, the refined oil can evaporate with a decrease in the yield of liquid products, or the formed hydrogen can be consumed again. In addition, there is also the problem of increasing the olefin or diene content as a result of thermal cracking.

[0031]

In addition, a pressure of 0.1 to 40 MPa is selected as the pressure condition at the cracking stage. If the pressure is less than 0.1 MPa, the reaction does not proceed sufficiently, or in some cases it is difficult to achieve a uniform flow of refined oil and water into the cracking reactor 1, and if the pressure exceeds 40 MPa, the cost of cracking reactor 1 may increase.

[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 split the double bond, thereby reducing the olefin or diene content.

[0033]

(Hydrogenation catalyst)

Here, in the cracking step, upstream of the hydrogenation step, the cracked hydrocarbon oil and hydrogen are obtained using water, and therefore water is contained in some cases in the cracked hydrocarbon oil. Accordingly, it is preferable to use as a hydrogenation catalyst to enable the hydrogenation reaction described above to proceed with a catalyst in which a metal having hydrogenation activity is supported on a support consisting of metal oxide that does not contain alumina (in particular γ-alumina) or silicon dioxide, causing large changes in the crystal structure of the catalyst under the influence of high temperature and high pressure steam, due to which p can not be used.

[0034]

An example of a metal oxide serving as a carrier that does not substantially degrade under the influence of water vapor may be, for example, zirconia or anatase type titanium dioxide (TiO ₂ ), or a mixture containing such an zirconia and anatase type titanium dioxide. The crystal structure of anatase-type titanium dioxide can be evaluated using, for example, X-ray diffraction analysis. In the case of anatase-type titanium dioxide, a diffraction peak appears (2θ = 25.5 °) corresponding to the (101) plane in the X-ray diffraction spectrum.

[0035]

As a metal (active metal) having hydrogenation activity, at least one metal from the group consisting of nickel, cobalt and molybdenum can be selected for deposition on the support described above. In this regard, from the point of view of ensuring sufficient hydrogenation efficiency, the total amount of zirconia or anatase-type titanium dioxide for mixing in the mixture forming the hydrogenation catalyst carrier is preferably 50% by weight. or more, more preferably 55% of the mass. or more, particularly preferably 60% of the mass. or more relative to the amount of the mixture.

In the case where a step for removing water from the cracked hydrocarbon oil is provided between the cracking step and the hydrogenation step to reduce the water content in the hydrocarbon oil, a hydrogenation catalyst can be used in which the active metal is supported on a carrier comprising γ-alumina or silica.

[0036]

(Reaction conditions)

The hydrogenation step using the hydrogenation catalyst described above is carried out under temperature conditions, for example, from 100 ° C to 374 ° C. Temperature conditions from 200 ° C to 350 ° C are preferably selected. If the temperature is below 100 ° C, the activation energy necessary for the reaction cannot be obtained, and therefore, the olefin or diene content cannot be sufficiently reduced. On the other hand, at temperatures exceeding 374 ° C, the hydrogenation reaction and thermal cracking can occur simultaneously, and therefore, cracked hydrocarbon oil can evaporate with a decrease in the yield of liquid products.

[0037]

In addition, with regard to pressure conditions in the hydrogenation step, a pressure equivalent to that existing before the cracking step is selected as the upper pressure limit, and a pressure value of 0.5 MPa is selected as the lower pressure limit, and a range of 1 is selected as a more preferred range. up to 5 MPa. If the pressure is less than 0.5 MPa, the reaction does not proceed sufficiently, or in some cases it is difficult to achieve a uniform supply of cracked hydrocarbon oil and hydrogen to the hydrogenation reactor 2. On the other hand, in the case where the hydrogenation step is carried out at a pressure higher than the pressure in the cracking step, a pressure-boosting operation or the like is necessary, and therefore, this case is not preferred. In addition, an undesirable reaction can occur, for example, a reaction in which the aromatic hydrocarbon core is hydrogenated in a hydrocarbon oil with excessive hydrogen consumption and coke deposition. In addition, the cost of the hydrogenation reactor 2 may increase.

[0038]

In this case, the reaction conditions described above are set in such a way as to meet the target values previously determined taking into account, for example, transportability and the like. heavy hydrocarbon oil, such as synthetic crude oil. As previously described, in Canada the concentration of olefins in pipeline specifications is limited to 1% or less, however this value varies depending on the characteristics of the crude oil, the weather conditions of the area where the synthetic crude oil is transported, etc., and therefore it is difficult to determine a constant value applicable in all cases.

[0039]

On the other hand, in the case where the hydrogenation reactions make it possible to proceed excessively, the aromatic hydrocarbon core is hydrogenated in the hydrocarbon oil, and therefore, hydrogen is excessively consumed, or coke can be deposited on the surface of the catalyst, and therefore, the catalyst can be inactivated, and therefore, such a case is undesirable. In addition, the amount of gas produced may increase with a corresponding decrease in the yield of the liquid product, and thus the need to lower the olefin or diene content to a value lower than the target value described above is low. In addition, if the progression of the hydrogenation reaction is limited to such an extent that the transportability described above can be achieved, the consumption of hydrogen can be reduced, and in addition, the decrease in the yield of the liquid product at the cracking stage is also suppressed, and thus the size can also be reduced. cracking reactor 1.

[0040]

The double bond located at the end of the main carbon chain or side chain has a higher reactivity than the double bond located on the inside of the end portion. Thus, it is believed that by hydrogenation of the terminal double bond, the polymerization of an olefin or diene can be significantly reduced.

In this case, in accordance with the molecular structure of the olefin or diene, a double bond located at the end of the main carbon chain or side chain can allow the hydrogenation reaction to proceed under milder conditions (low temperature, low pressure and low hydrogen / oil ratio) compared with a double bond located on the inside of the end portion. Thus, if the hydrogenation reaction is allowed to proceed under the most mild conditions, while achieving a predetermined target value by adjusting the conditions of the hydrogenation reaction in the light of this molecular structure, one can also find reaction conditions that can suppress the formation of gas to achieve a high yield of liquid product .

[0041]

In this regard, focusing on the position of the double bond in the cracked hydrocarbon after the hydrogenation reaction, an indicator is set indicating that the double bond at the end of the chain is smaller than on the inside, and the conditions of the hydrogenation reaction can be set so as to correspond this indicator. An example of such an indicator is A / B, if the ratio of the hydrogen content associated with the double bond in the end position of the diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is represented as A, and the ratio of the hydrogen content associated with the double the bond located on the inside from the end position to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is represented as B. In this regard, the relative content The hydrogen content can be determined using ¹ H-NMR.

[0042]

For example, the reaction conditions are set such that the A / B value is in the range from 0 to 0.5, preferably in the range from 0 to 0.3. As shown in the examples described below, if the A / B value exceeds 0.5, the olefin or diene content cannot be sufficiently reduced.

[0043]

Recycling Plant

Next, an example of a configuration of a processing plant in accordance with an embodiment will be described with reference to FIG. 2-5. In this case, the same reference numbers are used to designate the same devices in the respective processing plants in these figures.

FIG. 2 relates to the flow diagram shown in FIG. 1 (a), and illustrates a proposed hydrocarbon oil processing plant coupled to a refinement process 3 in which water is used to refine. In this example, the mixed fluid from the refined oil and water resulting from the refinement process 3 is supplied to the cracking reactor 1 through a pump 11 and a heating device 12, and brought into contact with the cracking catalyst, resulting in the formation of cracked hydrocarbon oil and hydrogen.

[0044]

After that, the mixed fluid containing these cracked hydrocarbon oil and hydrogen is cooled in a cooling device 13, free water is separated by a water / oil separator 14. The water collected in the sump of the water / oil separator 14 is discharged through the cooling device 15 and the flow control valve 16 and is reused, for example, in the refinement process 3. The separation of water from oil, carried out using a water / oil separator 14, corresponds to the stage of separation of water from a mixture of cracked hydrocarbon oil and hydrogen (stage separation of water / oil). If necessary, the provision of a water / oil separation stage (water / oil separator 14) can be omitted.

[0045]

The mixed fluid of cracked hydrocarbons and hydrogen, from which free water was separated by means of a water / oil separator 14, is supplied to the hydrogenation reactor 2 through a cooling device 21 and a pressure control valve 22 and comes into contact with the hydrogenation catalyst, thereby reducing the content olefin or diene. After that, a mixed fluid containing cracked hydrocarbons, a gas formed as a result of a hydrogenation reaction, a hydrogen residue, etc. enter the water / oil separator 25 through a cooling device 23 and a pressure control valve 24. Further, cracked hydrocarbons, separated from free water and gas, are discharged as synthetic crude oil having a low olefin or diene content.

[0046]

FIG. 3 relates to a flow diagram shown in FIG. 1 (b), and illustrates a proposed installation for processing cracked hydrocarbon oil, coupled to a refinement process 3 in which no water is used to refine. In this example, water is mixed with refined oil discharged from the refining process 3 through a pump 17 and a heating device 18, which differs from the refining unit shown in FIG. 2.

[0047]

Further, in FIG. 4, a case is illustrated in which the refined oil exiting the refining process 3 is subjected to fractional distillation in a distillation unit, and the fraction after fractional distillation is processed in a cracking step. In the example shown in FIG. 4, the mixed fluid from the refined oil and water resulting from the refinement process 3 and passing through the heating device 41 is fractionally distilled in the distillation column 42 and separated into a light fraction and a heavy fraction, and then the mixed fluid from the light fraction and water is processed into cracking reactor 1. As described previously, a fraction having a distillation temperature of 60-220 ° C. has a relatively high olefin or diene content, and therefore, the load on the cracking reactor 1 can be reduced by separating the heavy fraction having a low olefin or diene content and the rest fractions to the cracking stage.

[0048]

In this case, the use of the distillation column 42 is not limited to the case where the refined oil is divided into the following two fractions: a light fraction and a heavy fraction. For example, in the case where the intermediate fraction has a high olefin or diene content, the refined oil is divided into the following three fractions: a light fraction, an intermediate fraction and a heavy fraction, and the intermediate fraction can be processed at the cracking stage.

In addition, in the distillation apparatus shown in FIG. 4, a cooling device and the like is provided on the headstream side of the distillation column 42, however, a description thereof is omitted here.

[0049]

In FIG. 5 shows an example in which a refining unit according to this embodiment is proposed, connected to a supercritical water refining unit (see, for example, Japanese Patent Application Laid-Open No. 2011-88964), by which the refined oil is thermally cracked using supercritical water as one example of a refinement process 3.

Crude oil, such as superheavy crude oil, is supplied to the supercritical water treatment reactor 301 through a pump 302 and a heating device 303 at a temperature such that polycondensation does not occur, for example, at 300-450 ° C. On the other hand, water is supplied to the supercritical water treatment reactor 301 through the pump 304 and the heating element 305 at a temperature not lower than the supercritical temperature (374 ° C), for example, at 450-600 ° C.

[0050]

In a supercritical water treatment reactor 301, the pressure is 22.1 MPa (critical water pressure) or more, for example, from 25 MPa to 30 MPa, and the temperature is from 374 ° C to 500 ° C, and thermal cracking of the crude oil proceeds inside the reactor 301 supercritical water treatment. The resulting light oil component is recovered in the supercritical aqueous phase and fed to the cracking reactor 1. The light petroleum component is then subjected to a cracking step and a hydrogenation step, resulting in a cracked hydrocarbon oil having a reduced olefin or diene content and used as a raw material of synthetic crude oil, which is the same as in the case shown in FIG. 2. In addition, the water separated at each stage is recycled as a raw material for supercritical water through a recycle water tank 56 or a pipeline provided with a pump 57 or 19. The cracking step can be carried out by placing the cracking catalyst in a supercritical water treatment reactor 301, without cracking reactor 1 provided.

[0051]

On the other hand, a heavy oil component that cannot be extracted into supercritical water enters the evaporation drum 53 under pressure conditions from about 0.1 MPa to 8 MPa and temperature conditions from about 250 ° C to 430 ° C through a cooling device 51 and a control a flow valve 52, and water and the light oil component dissolved in the heavy oil component are separated by a single distillation. The water and the light oil component separated by a single distillation are separated from each other by a cooling device 54 and a water / oil separator 55, and the light oil component is used as a raw material of synthetic crude oil, and the water is recycled. In this case, the light oil component can be processed at the cracking stage and the hydrogenation stage to reduce the olefin or diene content.

A portion of the heavy oil component separated from the light oil component and the like in the evaporation drum 53 is mixed into the synthetic crude oil, and the rest serving as residual oil is used as fuel or the like for a heating furnace serving as a heating device 303 or 305.

[0052]

In accordance with this embodiment, the following beneficial effect is manifested. By using hydrogen obtained by bringing water and a hydrocarbon oil containing diene or olefin (e.g., refined oil obtained as a result of refining process 3) into contact with a cracking catalyst, a hydrogenation reaction of cracked hydrocarbon oil obtained with this hydrogen is carried out and, therefore, even in a situation where it is difficult to obtain hydrogen, a cracked hydrocarbon oil with a reduced content of diene or olefin can be obtained.

[0053]

In this case, in the example described above, focusing on reducing the olefin or diene content, which cause problems in the transportation of synthetic crude oil or the like, an example is given in which the refined oil removed from the refining process provided for in the well section processed at the cracking stage and the hydrogenation stage. However, if necessary, the application of the present invention to refined oil obtained as a result of a refining process at a refinery or the like is not ruled out.

Examples

[0054]

Refined Oil Characteristics

The characteristics of the refined oil used in the experiment described below are shown in Table 1. Quantitative determination of the ratio of the hydrogen content related to olefins (total H olefins) in the hydrocarbon oil to the total hydrogen content in the hydrocarbon oil was determined using proton NMR analysis (NMR spectrometer -500, manufactured by Varian, Inc.). Moreover, among the total H of olefins, hydrogen is bonded to carbon located at the end of the main carbon chain or side chain (end H of olefin) and hydrogen is bonded to carbon located on the inside of the carbon located at the end (inner H olefin), differ from each other based on the positions of the NMR peaks.

In Table 1, “CGO + LCO” means a blended oil consisting of cracked light oil (coking gas oil: CGO) obtained from a coking unit and light recycled gas oil (LCO) obtained from FCC. In addition, “oil refined with supercritical water” means refined oil (belonging to a light oil component and containing water) obtained by refining using a supercritical water treatment process in a supercritical water treatment reactor 301, illustrated by the example of FIG. 5.

Table 1 CGO + LCO Supercritical Water Refined Oil Specific gravity g / cm ³ 0.910 0.922 Elemental analysis S (X-ray fluorescence) % of the mass. 0.71 3.26 N (vacuum method) % of the mass. 0,061 0.149 Distillation Characteristics Below 180 ° C % of the mass. 5,0 7.0 180-270 ° C % of the mass. 52,5 19.0 270-360 ° C % of the mass. 41.0 33.0 360-540 ° C % of the mass. 1,5 37.0 Above 540 ° C % of the mass. 0,0 4.0 Diene number - 0.82 4.74

Proton NMR Results Aromatic hydrogen % H 16,4 5,4 H in the allylic position % H 23,2 14.3 N paraffins % H 53,2 65.3 N naphthenes % H 6.4 14.0 Total H olefins % H 0.7 1,0 Terminal H olefins % H 0.39 0.51 Internal H olefins % H 0.36 0.47

[0055]

(Experiment 1)

A study was conducted to determine how much the total content of H olefins in the refined oil was reduced by the hydrogenation step.

A. Experimental conditions

The refined oil having the characteristics shown in table 2 was processed at the cracking stage and the hydrogenation stage, and changes in the total H olefins were analyzed.

(Example 1-1)

Processing was carried out for CGO + LCO using an experimental setup having the same configuration as the processing setup shown in FIG. 3. A mixed metal oxide containing Zr as element X, Ce as element Y ₁ , and W as element Y ₂ , and having a value of x / (y ₁ + y2) = 1 and used as a catalyst in the cracking reactor 1, was used. y ₂ / y ₁ = 0.06. In addition, a catalyst was used as a hydrogenation catalyst in the hydrogenation reactor 2, in which Ni-Mo as active metals were supported on a support consisting of 100% by weight. anatase type titanium dioxide.

(Example 1-2)

Refining was carried out for refined oil obtained from a refining unit with supercritical water having the same configuration as the refining unit shown in FIG. 2. The structures of the cracking catalyst and the hydrogenation catalyst are the same as in Example 1-1 (the conditions for the catalysts are the same in the following corresponding examples).

table 2 CGO + LCO Supercritical Water Refined Oil Total H olefins % H 0.74 0.98 Terminal H olefins % H 0.39 0.51 Internal H olefins % H 0.36 0.47

<Reaction conditions>

Oil feed rate: 50 ml / h

(a) Cracking reaction

Temperature: 430 ° C, pressure: 25 MPa (g), water / oil ratio: 1.58 (mass ratio)

(b) Hydrogenation Reaction

Temperature: 100, 150, 200, 250, 300 and 350 ° С, pressure: 5 MPa (g).

[0056]

B. Experiment Results

In FIG. 6 is a graph showing the hydrogenation reaction temperature on the horizontal axis and the ratio [% H] of the total H olefins to total hydrogen in the oil after the reaction is shown on the vertical axis. Here, the total H olefin content was calculated by summing the relative hydrogen contents related to the terminal olefin and the internal olefin, respectively. In addition, the thin dashed line shows the total H of olefins in CGO + LCO as a baseline before hydrogenation, and the thick dashed line shows the total H of olefins in the refined oil obtained by refining with supercritical water before hydrogenation. In both cases, in Example 1-1 (CGO + LCO) and Example 1-2 (oil enriched with supercritical water), the total H olefin content decreased with increasing hydrogenation temperature. It was found that the H content of olefins was decreased by the hydrogenation step.

[0057]

(Experiment 2)

CGO + LCO was subjected to a cracking step and a hydrogenation step, and a change in the relative content of terminal H olefin or internal H olefin was analyzed.

A. Experimental conditions

(Example 2)

Processing was carried out using the same CGO + LCO mixture and the experimental setup as in Example 1-1.

<Reaction conditions>

Oil feed rate: 50 ml / h

(a) Cracking reaction

Temperature: 430 ° C, pressure: 25 MPa (g), water / oil ratio: 1.58 (mass ratio)

(b) Hydrogenation Reaction

Temperature: 100, 150, 200, 250, 300 and 350 ° С, pressure: 5 MPa (g).

[0058]

B. Experiment Results

In FIG. Figure 7 shows the ratio of [% H] of the terminal H olefin or internal H olefin to the total hydrogen content of the cracked hydrocarbon oil after the cracking step and the hydrogenation step CGO + LCO are carried out (hereinafter referred to as “obtained oil” for convenience). In FIG. 7, the temperature of the hydrogenation reaction is shown along the horizontal axis, and the relative contents of the terminal or internal H olefin are presented on the vertical axis. In the figure, the terminal H olefin (corresponding to the “relative hydrogen content A” within the scope of the claims) is shown by rhombuses, and the internal H olefin (corresponding to the “relative hydrogen B content” to the scope of the claims) is shown by triangles. In addition, the thin dashed line in the figure shows the end H of the olefin in CGO + LCO as the baseline before refining, and the thick dashed line shows the internal H of the olefin in the same oil before refining as the baseline (the same will apply to Fig. 9, Fig. 10 and Fig. 12 in relation to the horizontal axis, vertical axis and legend).

Further, from the obtained relative content of terminal H olefin and relative content of internal H olefin, the ratio of terminal H olefin to internal H olefin was calculated (corresponding to the value “A / B” within the scope of the claims), and in FIG. 8 shows a graph in which the obtained values are plotted relative to the temperature of the hydrogenation reaction. In FIG. 8, the temperature of the hydrogenation reaction is represented on the horizontal axis, and the ratio of the terminal H olefin to the internal H olefin is presented on the vertical axis (the same will apply to Fig. 11 with respect to the horizontal axis and vertical axis).

[0059]

As follows from FIG. 7, under low temperature conditions from 100 ° C to 200 ° C, as the temperature of the hydrogenation reaction increased, the content of terminal H olefin rapidly decreased, but the content of internal H olefin did not decrease. In addition, under conditions at 200 ° C. or less, the relative content of internal H olefin was higher than in the CGO + LCO mixture used as a raw material. It is believed that this is due to the fact that part of the terminal H olefin changed its position and became the internal H olefin, as a result of which the relative content of internal H olefin increased compared to the relative content in the raw material. In addition, when extrapolating the results shown in FIG. 7, it is assumed that, at temperatures below 100 ° C, both the terminal olefin and the internal olefin are practically not subjected to hydrogenation.

[0060]

Under conditions in which the temperature of the hydrogenation reaction ranged from 250 ° C to 350 ° C, with increasing temperature, the content of terminal H olefin and the content of internal H olefin decreased. On the other hand, when the temperature rises to high values in excess of 350 ° C., it is expected that there will be a problem in that the hydrogenation of the aromatic ring core leads to an increase in hydrogen consumption, or a hydrocarbon having a low boiling point such as methane is formed, which will lower the yield of liquid product.

[0061]

Further, when the change in the value of the ratio of the terminal H olefin to the internal H olefin shown in FIG. 8, under low-temperature conditions, in which the temperature of the hydrogenation reaction ranged from 100 ° C to 200 ° C, as the temperature increased, the ratio of the terminal H olefin to internal H olefin rapidly decreased. This is because the transition of the internal H olefin was essentially constant, however, the content of the terminal H olefin significantly decreased with increasing temperature. It is shown that under such temperature conditions the internal olefin is practically not hydrogenated, while the terminal olefin is hydrogenated.

[0062]

On the other hand, there was a tendency that the ratio of the terminal H olefin to internal H olefin decreased with increasing temperature also at temperatures from 250 ° C to 350 ° C, but the degree of decrease was small. It is assumed that simultaneously with the hydrogenation of the terminal olefin, the internal olefin was also hydrogenated, and thus the reduction was small. On the other hand, it is believed that the reason why the decreasing tendency was nevertheless observed was due to the fact that the decrease in the internal olefin was slower than in the terminal olefin.

[0063]

Based on the results shown in FIG. 8, it was found that the terminal olefin is hydrogenated more easily than the internal olefin. On the other hand, based on the results shown in FIG. 7, it is assumed that the terminal olefin is not hydrogenated under conditions where the temperature is below 100 ° C, and therefore, it can be said that when the ratio of the terminal H olefin to internal H olefin is 0.5 or more, the terminal olefin does not sufficiently hydrogenated.

[0064]

(Experiment 3)

The oil enriched with supercritical water was subjected to a cracking step and a hydrogenation step, and a change in the relative content of terminal H olefin or internal H olefin was analyzed.

A. Experimental conditions

(Example 3)

Used the same oil, ennobled with supercritical water, as in example 1-2. In addition, in the experimental setup used for refining oil refined with supercritical water, a cooling device 13 and a water / oil separator 14 were not provided downstream of the cracking reactor 1, which differs from the refining unit shown in FIG. 2.

<Reaction conditions>

Oil feed rate: 50 ml / h

(a) Water cleavage reaction

Temperature: 430 ° C, pressure: 25 MPa (g), water / oil ratio: 1.58 (mass ratio)

(b) Hydrogenation Reaction

Temperature: 200, 250 and 300 ° С, pressure: 5 MPa (g.).

[0065]

B. Experiment Results

In FIG. 9 shows the ratio of [% H] of the terminal H olefin or internal H olefin to the total hydrogen in the resulting oil after the cracking step and the hydrogenation step of the oil enriched with supercritical water.

As follows from FIG. 9, in the temperature range 200-300 ° C, the relative content of the terminal H olefin was substantially reduced, and it was confirmed that even in the case where a water-oil separation step was not provided before the hydrogenation step, the H content of olefins could be reduced.

[0066]

(Experiment 4)

The oil enriched with supercritical water was subjected to a cracking step and a hydrogenation step, and a change in the relative content of terminal H olefin or internal H olefin was analyzed.

A. Experimental conditions

(Example 4)

Refining was carried out using the same oil, ennobled with supercritical water, and the experimental setup as in example 1-2.

<Reaction conditions>

Oil feed rate: 50 ml / h

(a) Cracking reaction

Temperature: 430 ° C, pressure: 25 MPa (g), water / oil ratio: 1.58 (mass ratio)

(b) Hydrogenation Reaction

Temperature: 100, 150, 200, 250, 300 and 350 ° С, pressure: 5 MPa (g).

[0067]

B. Experiment Results

The ratio [% H] of the terminal H olefin or internal H olefin content to the total hydrogen content of the obtained oil after the cracking step and the hydrogenation step of the oil enriched with supercritical water are shown in FIG. 10, and a change in the ratio of terminal H olefin to internal H olefin is shown in FIG. eleven.

As follows from FIG. 10, practically the same tendency was observed with respect to the change in the relative content of the terminal H olefin or internal H olefin depending on the temperature of the hydrogenation reaction, as in the case of Example 2 shown in FIG. 7 (in the case when the same treatment was performed for CGO + LCO). In addition, with respect to the ratio of terminal H olefin to internal H olefin, the same tendency was also observed as was observed in Example 2 shown in FIG. 8.

[0068]

(Experiment 5)

The light fraction (lighter than light oil (distillation characteristics: 360 ° C or lower)) obtained by distillation of the oil refined with supercritical water using a distillation unit was subjected to a cracking stage and a hydrogenation stage, and the change in the relative content of the terminal H was analyzed olefin or internal H olefin.

A. Experimental conditions

(Example 5)

The refining was carried out using the same oil refined with supercritical water as in Example 1-2, and also using an experimental setup having the same configuration as the refining setup shown in FIG. four.

The relative content of the terminal H olefin or internal H olefin included in the light fraction is shown in table 3.

Table 3 Terminal H olefin % H 0.94 Internal H olefin % H 0.87

<Reaction conditions>

Oil feed rate: 50 ml / h

(a) Cracking reaction

Temperature: 430 ° C, pressure: 25 MPa (g), water / oil ratio: 1.58 (mass ratio)

(b) Hydrogenation Reaction

Temperature: 200, 250 and 300 ° С, pressure: 5 MPa (g.).

[0069]

B. Experiment Results

In FIG. 12 shows the ratio of [% H] of the terminal H olefin or internal H olefin to the total hydrogen content of the obtained oil after the cracking step and the hydrogenation step of the light fraction obtained by distillation of the oil refined with supercritical water.

According to FIG. 12, it was confirmed that also when the light fraction obtained from the distillation of oil refined with supercritical water was used as a raw material, the content of H olefins decreased. It becomes possible to increase the amount of crude oil that can be processed using the refinement process, and to reduce the amount of catalyst used by sending to the cracking stage and the hydrogenation stage part of the fraction obtained by distillation after the refinement process.

The trend noted in the examples described above also applies to the case in which the combination of elements X, Y ₁ and Y _{2 of the} cracking catalyst changes, the value x / (y ₁ + y ₂ ) or y ₂ / y ₁ , the relative content of titanium dioxide in a hydrogenation catalyst, a type of active metal or the like. Thus, the technical scope of the invention is not limited to the case where the cracking catalyst and the hydrogenation catalyst used in the examples described above are used.

List of Reference Items

[0070]

1: cracking reactor

14: water / oil separator

2: hydrogenation reactor

3: refinement process

301: supercritical water treatment reactor

42: distillation column

Claims (32)

1. A method of processing hydrocarbon oil, including: the step of producing cracked hydrocarbon oil and hydrogen by bringing water and a hydrocarbon oil containing at least one diene and olefin compound into contact with the cracking catalyst at a temperature of 375-550 ° C. to effect cracking; and a step of reducing the content of at least one diene and olefin compound by bringing hydrogen and cracked hydrocarbon oil obtained in the previous step into contact with a hydrogenation catalyst at a temperature of 100-374 ° C. to carry out a hydrogenation reaction of cracked hydrocarbon oil; moreover, the hydrogenation reaction is carried out in such a way that if the ratio of the hydrogen content associated with the terminal carbon-carbon double bond of a diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is denoted as A and the ratio of the hydrogen content associated with the internal carbon-carbon double the bond of a diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is denoted as B, then the A / B value is in the range of t 0 to 0.5. 2. A method of processing a hydrocarbon oil according to claim 1, characterized in that the method further includes the step of separating water from the mixture containing cracked hydrocarbon oil and water after contacting with a cracking catalyst, wherein the hydrogenation reaction is carried out for the cracked hydrocarbon oil after separation of water . 3. A method of processing a hydrocarbon oil according to claim 1 or 2, characterized in that the hydrocarbon oil contains refined oil obtained by refining the crude oil using water, the water used to produce hydrogen using a cracking catalyst is water taken together with refined oil. 4. A method for processing hydrocarbon oil according to claim 1 or 2, characterized in that the hydrocarbon oil contains refined oil obtained by bringing the crude oil into contact with supercritical water. 5. A method of processing a hydrocarbon oil according to claim 3, characterized in that the hydrocarbon oil contains at least one fraction obtained by dividing the enriched oil into a number of fractions having different boiling temperature ranges by distillation. 6. A method for processing hydrocarbon oil according to claim 1 or 2, characterized in that the cracking catalyst is a mixed metal oxide, which contains: (a) one element X selected from elements of group IVA; (b) one element Y ₁ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₁ is an element other than element X); and (c) one element Y ₂ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₂ is an element other than element X and element Y ₁ ); and in which (d) the ratio of the content x of the element X to the sum (y ₁ + y ₂ ) of the content of y _{1 of the} element Y ₁ and the content of _{2 of the} element Y ₂ is 0.5 or more and 2.0 or less, and (e) the ratio of the content of y ₂ element Y ₂ to the content y _{1 of} element Y ₁ is 0.02 or more and 0.25 or less. 7. The method of processing hydrocarbon oil according to claim 6, characterized in that element X is Zr, element Y ₁ is Ce, and element Y ₂ is an element selected from the group of elements Y ₂ consisting of W, Fe and Mn. 8. A method of processing a hydrocarbon oil according to claim 1 or 2, characterized in that the hydrogenation catalyst is made in such a way that a metal having hydrogenation activity is supported on a carrier consisting of metal oxide, which does not include alumina or silicon dioxide. 9. The method of processing hydrocarbon oil according to claim 8, characterized in that the hydrogenation catalyst is made in such a way that at least one metal selected from the group consisting of nickel, cobalt and molybdenum is supported on a carrier containing zirconia or titanium dioxide anatase type. 10. Installation for the processing of hydrocarbon oil, including: a cracking reactor that is supplied with water and a hydrocarbon oil containing at least one diene and olefin compound and loaded with a cracking catalyst that produces cracked hydrocarbon oil and hydrogen from hydrocarbon oil and water; and a hydrogenation reactor, which is supplied with hydrogen obtained in the cracking reactor and cracked hydrocarbon oil leaving (flowing out) from the cracking reactor, and loaded with a hydrogenation catalyst, which reduces the content of at least one of the diene and olefin compounds, allowing the cracked hydrogenation reaction to occur hydrocarbon oil moreover, the hydrogenation reaction is carried out in such a way that if the ratio of the hydrogen content associated with the terminal carbon-carbon double bond of a diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is denoted as A and the ratio of the hydrogen content associated with the internal carbon-carbon double the bond of a diene or olefin to the hydrogen content in the cracked hydrocarbon oil after the hydrogenation reaction is denoted as B, then the A / B value is in the range of t 0 to 0.5. 11. Installation for processing hydrocarbon oil according to claim 10, characterized in that the installation further includes an oil and water separator, in which water is separated from the mixture containing water and cracked hydrocarbon oil flowing from the cracking reactor, and cracked hydrocarbon oil after separating water in an oil and water separator is fed to a hydrogenation reactor. 12. Installation for processing hydrocarbon oil according to claim 10 or 11, characterized in that the hydrocarbon oil contains refined oil obtained from the refining unit, which ennobles the crude oil using water, and the water used to produce hydrogen using a cracking catalyst is water discharged with refined oil. 13. Installation for processing hydrocarbon oil according to claim 10 or 11, characterized in that the hydrocarbon oil contains refined oil obtained from a refining unit with supercritical water, which ennobles the crude oil by bringing the crude oil into contact with supercritical water. 14. Installation for processing hydrocarbon oil according to claim 12, characterized in that the hydrocarbon oil contains at least one fraction obtained from a distillation unit, which divides the enriched oil into a number of fractions having different boiling temperature ranges by distillation. 15. Installation for the processing of hydrocarbon oil according to claim 10 or 11, characterized in that the cracking catalyst is a mixed metal oxide, which contains: (a) one element X selected from elements of group IVA; (b) one element Y ₁ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₁ is an element other than element X); and (c) one element Y ₂ selected from the group consisting of elements of group IIIA, elements of group VIA, elements of group VIIA, elements of group IVA in 4-6 periods and elements of group VIII in 4 periods (provided that element Y ₂ is an element other than element X and element Y ₁ ); and in which (d) the ratio of the content x of the element X to the sum (y ₁ + y ₂ ) of the content y _{1 of the} element Y ₁ and the content of the ₂ element Y ₂ is 0.5 or more and 2.0 or less, and (e) the ratio of the content of y ₂ element Y ₂ to the content y _{1 of} element Y ₁ is 0.02 or more and 0.25 or less. 16. Installation for the processing of hydrocarbon oil according to p. 10 or 11, characterized in that the hydrogenation catalyst is made in such a way that the metal having hydrogenation activity is supported on a carrier consisting of metal oxide, which does not include alumina or silicon dioxide .

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