WO2014054234A1 - 炭化水素油の処理方法及び炭化水素油の処理装置 - Google Patents
炭化水素油の処理方法及び炭化水素油の処理装置 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
Definitions
- the present invention relates to a technique for reducing olefins and dienes contained in hydrocarbon oil.
- the dilution method has a problem that a sufficient diluent such as condensate must be secured, and a problem that the transportation cost increases because the transportation amount increases by the amount of dilution.
- the reforming method requires a large-scale refinery-like plant at the well site, so there is a problem that it is economical only in the vicinity of large-scale oil fields, and processing of by-products such as coke and sulfur. In some cases, there is a problem that hydrogen necessary for reforming must be secured.
- the present inventors can modify heavy crude oil or ultraheavy crude oil using a simple scheme at the base of the well using supercritical water, and can transport the pipeline without requiring a diluent.
- Development of technology for producing synthetic crude oil has undergone a thermal history, and hydrocarbons in the oil are decomposed to produce unsaturated hydrocarbons, resulting in high concentrations of olefins and dienes. If the concentration of olefin or diene is high, the stability of the oil is low, and there is a risk that the polymer will be polymerized during transportation, causing the polymer to settle in the pipeline or cause problems such as clogging.
- the line specification defines an olefin concentration of 1% or less. These olefins and dienes can be reduced by a hydrogenation reaction, but for that purpose, it is necessary to secure hydrogen, and when there is no hydrogen production facility nearby such as at the well, it is usually difficult to obtain natural gas or naphtha. It is necessary to construct a facility for producing hydrogen from the raw material. However, the construction of such a hydrogen production facility leads to an increase in construction costs, and there are problems that there are areas where it is difficult to obtain natural gas and naphtha as raw materials.
- cracked oil produced by FCC equipment, coker equipment, etc. has a relatively high concentration of olefins, and these olefins generate sludge in transportation pipes or refined oil tanks, and blockage, etc. It can be a cause. For this reason, it may be necessary to remove the olefin content in the cracked oil, but the conventional hydrorefining has a problem of consuming useful hydrogen in the station.
- the hydrocarbon oil is lightened by proceeding with the decomposition reaction of the hydrocarbon oil in the presence of a catalyst or in a supercritical state of water with respect to the mixture of the hydrocarbon oil and water.
- JP 2008-297466 A Claim 1, paragraph 0017 JP 2009-242467 A: Claim 1, paragraph 0028 JP 2006-7151 A: Claim 1, paragraphs 00170009 to 0010
- the present invention has been made under such circumstances, and the object thereof is a hydrocarbon oil capable of reducing the content of dienes and olefins in the hydrocarbon oil even when it is difficult to obtain hydrogen. And a processing apparatus for hydrocarbon oil.
- the hydrocarbon oil processing method is a hydrocarbon oil processing method, A step of producing a cracked hydrocarbon oil and hydrogen by cracking a hydrocarbon oil containing at least one of diene and olefin and water by contacting them with a cracking catalyst at a temperature of 375 to 550 ° C .; Next, the hydrogen and the cracked hydrocarbon oil are brought into contact with a hydrogenation catalyst at a temperature of 100 to 374 ° C., and the hydrogenation reaction of the cracked hydrocarbon oil is performed to reduce the content of at least one of diene and olefin. And a step of performing.
- the method for treating hydrocarbon oil may have the following characteristics. (1) It has the process of isolate
- the hydrocarbon oil includes a reformed oil obtained by reforming raw material oil using water, and the water that generates hydrogen by the cracking catalyst is water discharged together with the reformed oil. thing. Moreover, the said hydrocarbon oil contains the reformed oil obtained by making raw material oil contact supercritical water. Further, the hydrocarbon oil contains at least one fraction obtained by distilling the reformed oil and separating it into a plurality of fractions having different boiling ranges.
- the ratio of the amount of hydrogen of the carbon-carbon double bond at the end of the diene and olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is A
- the ratio of the hydrogen amount of the double bond is B
- the A / B value should be in the range of 0 to 0.5.
- the cracking catalyst is (A) one element X selected from group IVA elements; (B) one element Y 1 selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Is an element different from the element X), (C) One element Y 2 selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Element X and element Y 1 are different elements).
- the element X is an element selected from the group Y 2 consisting of Zr
- the element Y 1 is Ce
- the element Y 2 is W, Fe, or Mn.
- the hydrogenation catalyst is obtained by supporting a metal having hydrogenation activity on a carrier made of a metal oxide not containing alumina and silica.
- the hydrogenation catalyst is one in which one or more metals selected from the group consisting of nickel, cobalt, and molybdenum are supported on a support containing zirconia or anatase titania.
- a hydrocarbon oil processing apparatus is a hydrocarbon oil processing apparatus, A cracking reaction tower charged with a hydrocarbon oil containing at least one of a diene and an olefin, and water, and charged with the hydrocarbon oil and a cracking hydrocarbon oil and a cracking catalyst for generating hydrogen from the water; Hydrogen produced in the cracking reaction tower and cracked hydrocarbon oil flowing out from the cracking reaction tower are supplied, and hydrogenation reaction of the cracked hydrocarbon oil proceeds to contain at least one of diene and olefin And a hydrogenation reaction column filled with a hydrogenation catalyst for reducing the amount.
- the said hydrocarbon oil processing apparatus may be provided with the following characteristics. (6) An oil / water separation tank for separating water from a mixture containing cracked hydrocarbon oil and water flowing out from the cracking reaction tower is provided, and water is separated in the hydrogenation reaction tower in the oil / water separation tank. The cracked hydrocarbon oil after being supplied. (7) The hydrocarbon oil includes reformed oil obtained from a reformer that reforms the raw material oil using water, and the water that generates hydrogen by the cracking catalyst was discharged together with the reformed oil. Be water. In addition, the hydrocarbon oil includes reformed oil obtained from a supercritical water reformer that reforms supercritical water in contact with raw material oil.
- the hydrocarbon oil contains at least one fraction obtained from a distillation apparatus that distills the reformed oil and separates it into a plurality of fractions having different boiling ranges.
- the ratio of the amount of hydrogen of the carbon-carbon double bond at the end of the diene and olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is A
- the ratio of the hydrogen amount of the double bond is B
- the A / B value should be in the range of 0 to 0.5.
- the cracking catalyst is (A) one element X selected from group IVA elements; (B) one element Y 1 selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Is an element different from the element X), (C) One element Y 2 selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Element X and element Y 1 are different elements).
- the hydrogenation catalyst is obtained by supporting a metal having hydrogenation activity on a carrier made of a metal oxide not containing alumina and silica.
- hydrogen produced by bringing a hydrocarbon oil containing a diene or olefin into contact with a cracking catalyst together with water is used to perform a hydrogenation reaction of the cracked hydrocarbon oil obtained together with this hydrogen. Even under circumstances where it is difficult to obtain hydrogen, it is possible to obtain a cracked hydrocarbon oil with a reduced content of dienes and olefins. Further, the amount of hydrogen to be produced can be adjusted by the content of dienes and olefins in the hydrocarbon oil to be treated.
- Embodiments of the present invention provide at least an olefin containing one carbon-carbon double bond (hereinafter simply referred to as a double bond) or a diene containing two double bonds in the molecular structure of the hydrocarbon.
- a double bond olefin containing one carbon-carbon double bond
- a diene containing two double bonds in the molecular structure of the hydrocarbon.
- the hydrocarbon may be a chain hydrocarbon, or a naphthene hydrocarbon or an aromatic hydrocarbon.
- the carbon skeleton may have a double bond, or the side chain may have a double bond.
- naphthenic hydrocarbons and aromatic hydrocarbons double bonds in side chains bonded to naphthene rings, aromatic rings, and condensed rings thereof are to be treated.
- hydrocarbons may contain atoms such as oxygen, nitrogen and sulfur.
- attention is focused on a relatively low-molecular hydrocarbon containing one or two double bonds, and the double bond is reduced.
- the content of double bonds in hydrocarbons containing heavy bonds may be reduced.
- Olefins and dienes are contained in hydrocarbon oils that have undergone a thermal history, and the thermal history is added during processing such as a process for lightening feedstock by removing or decomposing heavy components.
- thermal history examples include coker, FCC (Fluid Catalytic Cracking), Yurica (registered trademark), CPJ, aqua conversion, heated feed oil that performs pyrolysis of feedstock in the presence of steam (water)
- a supercritical water treatment in which a light oil thermally decomposed by bringing the oil into contact with supercritical water is extracted into supercritical water.
- Raw oils processed in these processes include heavy crude oils such as Middle Eastern oils, heavy oils such as atmospheric and vacuum residues of heavy crude oils, Canadian oil sand bitumen and Venezuelan orinocotal. There is super heavy crude oil.
- the hydrocarbon oil obtained by processing the raw material oil by a reforming process such as supercritical water treatment is called a reformed oil.
- the reformed oil contains a relatively large amount of olefin and diene in a fraction having a distillation temperature of 60 to 220 ° C., for example.
- These olefins and dienes can be reduced by a hydrogenation reaction that cleaves the carbon-carbon bond.
- the present inventors generate hydrogen by catalytic reaction with reformate using water that can be easily obtained at the well, etc., and use the hydrogen to generate olefins and dienes in the reformed oil. Has led to the development of technology to reduce the risk.
- FIGS. 1A and 1B are schematic flow diagrams of processes according to the embodiment.
- the reformed oil that flows out from the reforming process 3 and contains olefin and diene and water are supplied to the cracking reaction tower 1 and contact with the cracking catalyst to produce cracked hydrocarbon oil and hydrogen.
- These cracked hydrocarbon oil and hydrogen are supplied to the hydrogenation reaction tower 2 and brought into contact with the hydrogenation catalyst to reduce the contents of olefin and diene by the hydrogenation reaction (hydrogenation step).
- the cracked hydrocarbon oil having a low olefin and diene content obtained from the hydrogenation reaction tower 2 is used as a raw material for synthetic crude oil.
- the cracking reaction tower 1 is filled with a cracking catalyst
- the hydrogenation reaction tower 2 is filled with a hydrogenation catalyst.
- the method of bringing each catalyst into contact with reformed oil or cracked hydrocarbon oil is applied to a fixed bed. Not only the case of passing these fluids, but a suitable method such as a fluidized bed type or a boiling bed type may be adopted.
- the reforming process 3 for example, the above-mentioned CPJ, yurika, aqua conversion, supercritical water treatment, etc.
- the water supplied to the reforming process 3 and discharged from the reforming process 3 together with the reforming oil can be used as water for generating hydrogen.
- water is supplied to the cracking reaction tower 1 separately from the reformed oil from the reforming process 3 (FIG. 1 ( b)).
- the reformed oil and water are brought into contact with the cracking catalyst to decompose the reformed oil and water to obtain cracked hydrocarbon oil and hydrogen.
- the reaction for decomposing the reformed oil and water for example, the reformed oil is decomposed using lattice oxygen in oxides contained in the cracking catalyst, while the cracking catalyst contains a water cracking catalyst. Decompose water and replenish oxygen in lattice defects. Hydrogen is generated by this water splitting, and these cracked hydrocarbons and hydrogen are sent to the hydrogenation step.
- Decomposition catalyst As the decomposition catalyst for causing the above reaction to proceed, for example, a composite metal oxide that is an oxide formed by combining two or more metal oxides can be used. Specifically, a composite metal oxide containing predetermined elements X, Y 1 and Y 2 can be used as a decomposition catalyst. The crystal structure of the composite metal oxide used as the decomposition catalyst can be evaluated using, for example, X-ray diffraction analysis.
- predetermined element X a predetermined element Y 1, as the complex metal oxide containing predetermined element Y 2, (A) one element X selected from group IVA elements; (B) one element Y 1 selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Is an element different from the element X), (C) One element Y 2 selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Element X and element Y 1 are different elements).
- a composite metal oxide containing these three kinds of metal elements in a predetermined ratio can be given.
- the “predetermined ratio” for example, the ratio (molar ratio) of the abundance of each element X, Y 1 , Y 2 in the catalyst determined by melting / ICP-AES method, (D) a ratio of abundance x of the element X to the total (y 1 + y 2) between the abundance y 2 abundance y 1 and the element Y 2 elements Y 1 is 0.5 to 2.0 (0 .5 ⁇ x / (y 1 + y 2 ) ⁇ 2.0) (E) a ratio of abundance y 2 elements Y 2 relative abundance y 1 element Y 1 is 0.02 to 0.25 (0.02 ⁇ y 2 / y 1 ⁇ 0.25), A ratio can be mentioned.
- the composite metal oxide used as the decomposition catalyst is not limited to a specific element as long as it has the above-mentioned requirements.
- Specific examples of the element X, the element Y 1 , and the element Y 2 include Ti, Examples thereof include Zr, Ce, W, Mn, and Fe.
- the composite metal oxide in which these elements are element X, element Y 1 or element Y 2 is, for example, a composite containing Zr as element X, Ce as element Y 1 , W, Fe or Mn as element Y 2. Mention may be made of metal oxides. While oxides of the elements Y 2 in this example decomposes the reformate, oxide of the element X is decomposing water, oxides of the elements Y 1 suppresses the deterioration of the catalyst.
- the element X, the element Y 1, the composite metal oxide containing element Y 2, it is particularly preferable element X is zirconium (Zr). This is because if the element X is Zr, the structure of the composite metal oxide can be maintained even when the catalyst is used under high temperature and high pressure conditions. That is, in the complex metal oxide (decomposition catalyst) in which the element X is composed of Zr, hydrothermally synthesized zeolite, silica, or hydrogenation catalyst composed of ⁇ -alumina used for hydrocracking of hydrocarbon oil. In this way, the crystal structure of the catalyst is not significantly changed by high-temperature and high-pressure steam so that the catalyst cannot be used.
- Zr zirconium
- the catalyst is hardly deteriorated, and it is not necessary to pretreat the hydrocarbon oil (desulfurization and denitrogenation).
- 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 0.55 or more. It is preferable that it is 0.60 or more.
- the above-described composite metal oxide can be prepared using a known method such as a coprecipitation method or a sol-gel method.
- the composite metal oxide can be prepared as follows without any particular limitation.
- the obtained precipitate is filtered and dried, and then the dried precipitate is fired to obtain a composite metal oxide.
- the temperature for drying the precipitate in (iii) is preferably 100 ° C. or higher from the viewpoint of efficiently evaporating moisture, and 160 ° C. or lower from the viewpoint of preventing rapid drying. preferable.
- the temperature at which the dried precipitate is calcined is the structural stability of the resulting composite metal oxide (catalyst) (ie, suppression of structural change of the composite metal oxide when hydrocarbon oil is decomposed using the catalyst). From the viewpoint of the above, it is preferably 500 ° C. or higher, and from the viewpoint of suppressing the reduction of the surface area of the composite metal oxide to be generated, it is preferably 900 ° C. or lower.
- a catalyst that does not include the element Y 1 but includes a metal complex oxide of two kinds of elements of Zr as the element X and Fe as the element Y 2 and alumina may be used.
- a catalyst containing a metal oxide of Zr or Ti as the element X and alumina used for hydrocracking of hydrocarbon oil can be used.
- the decomposition step using the decomposition catalyst is performed under a temperature condition of, for example, 375 to 550 ° C., and a temperature condition of preferably 390 to 500 ° C. is selected. If the temperature is lower than 375 ° C., the water does not enter a supercritical state, and activation energy necessary for the reaction may not be obtained and sufficient hydrogen may not be obtained. In addition to the generation of more hydrogen than necessary, the reformed oil may be gasified due to the progress of thermal decomposition and the liquid yield may be reduced, or the generated hydrogen may be consumed again. Moreover, there is a concern that the content of olefins and dienes increases due to thermal decomposition.
- a pressure condition of 0.1 to 40 MPa is selected as the pressure condition of the decomposition process.
- the pressure is less than 0.1 MPa, the reaction may not proceed sufficiently, or it may be difficult to smoothly flow the reformed oil and water into the decomposition reaction tower 1. In addition, the production cost of the decomposition reaction tower 1 may be increased.
- Hydrogenation catalyst In the cracking process on the upstream side of the hydrogenation process, since cracked hydrocarbon oil and hydrogen are produced using water, moisture may be contained in the cracked hydrocarbon oil. Therefore, as a hydrogenation catalyst for proceeding with the hydrogenation reaction described above, alumina (particularly ⁇ -alumina) or a metal oxide containing no silica, in which the catalyst crystal structure is greatly changed by high-temperature and high-pressure steam and the catalyst cannot be used. It is preferable to use a support made of a material carrying a metal having hydrogenation activity.
- Examples of the metal oxide that becomes a carrier that is not easily deteriorated by water vapor include zirconia and anatase-type titanium dioxide (TiO 2 ), or a mixture containing these zirconia and anatase-type titanium dioxide.
- the metal having hydrogenation activity (active metal) supported on the carrier one or more metals selected from the group consisting of nickel, cobalt, and molybdenum can be selected.
- the total amount of zirconia and anatase-type titanium dioxide mixed in the mixture constituting the carrier of the hydrogenation catalyst is preferably 50% by mass or more of the mixture, More preferably, it is 55 mass% or more, and it is especially preferable that it is 60 mass% or more.
- a process for removing moisture in the cracked hydrocarbon oil is provided between the cracking process and the hydrogenation process, and if the moisture in the hydrocarbon oil can be reduced, ⁇ -alumina or silica is included as a carrier. You may use the hydrogenation catalyst which carry
- reaction conditions The hydrogenation step using the hydrogenation catalyst is performed under a temperature condition of 100 to 374 ° C., for example, and a temperature condition of 200 to 350 ° C. is preferably selected. If the temperature is less than 100 ° C., the activation energy required for the reaction cannot be obtained, and the content of olefins and dienes may not be sufficiently reduced. The decomposition proceeds, and the cracked hydrocarbon oil may be gasified to lower the liquid yield.
- the upper limit is selected to be the same as the pressure in the preceding decomposition process
- the lower limit is selected to be 0.5 MPa
- the more preferable range is 1 to 5 MPa.
- the pressure is less than 0.5 MPa
- the reaction may not proceed sufficiently, or it may be difficult to smoothly flow the cracked hydrocarbon oil and hydrogen into the hydrogenation reaction tower 2.
- the hydrogenation step is performed at a pressure exceeding the pressure in the decomposition step, it is not preferable because a pressure increasing operation or the like is required.
- nuclear hydrogenation of aromatic hydrocarbons in the hydrocarbon oil proceeds, and there is a possibility that undesirable reactions such as excessive consumption of hydrogen and precipitation of coke may proceed.
- the manufacturing cost of the hydrogenation reaction tower 2 may be increased.
- the above-mentioned reaction conditions are set so as to satisfy a preset target value in consideration of, for example, transportability of heavy hydrocarbon oil such as synthetic crude oil.
- a preset target value in consideration of, for example, transportability of heavy hydrocarbon oil such as synthetic crude oil.
- the olefin concentration is defined as 1% or less as a pipeline specification, but this value varies depending on the properties of the feedstock and the weather conditions in the area where the synthetic crude is transported. It is difficult to set a uniform value.
- the hydrogenation reaction proceeds excessively, the nuclear hydrogenation of aromatic hydrocarbons in the hydrocarbon oil proceeds, hydrogen is consumed excessively, and coke is easily deposited on the catalyst surface.
- the catalyst may be deactivated, which is undesirable.
- the amount of gas generated may increase and the liquid yield may decrease, there is little need to reduce the olefin or diene content beyond the above-mentioned target value.
- the hydrogenation reaction proceeds to such an extent that the transportability can be ensured, the amount of hydrogen consumption can be reduced, and a decrease in the liquid yield can be suppressed even in the decomposition step, and the decomposition reaction tower 1 can be downsized. it can.
- the double bond located at the end of the carbon skeleton or side chain is more reactive than the double bond located on the inner side of the end. Therefore, it is considered that the polymerization reaction of olefin and diene can be greatly reduced by hydrogenating the terminal double bond.
- the double bond located at the end of the carbon skeleton or side chain is more gentle than the double bond located on the inner side of the terminal (
- the hydrogenation reaction can proceed under low temperature, low pressure, low hydrogen / oil ratio). Therefore, if the hydrogenation reaction conditions are adjusted from the viewpoint of this molecular structure and the hydrogenation reaction can proceed under the mildest conditions while satisfying the preset target values, the generation of gas can be suppressed. It is also possible to search for reaction conditions with a high liquid yield.
- the reaction conditions for the hydrogenation reaction may be set as follows.
- the ratio of the hydrogen amount of the double bond at the terminal position of the diene or olefin to the amount of hydrogen in the cracked hydrocarbon oil after the hydrogenation reaction is A, which is located on the inner side of the terminal position.
- a value of A / B can be exemplified when the ratio of the hydrogen amount of the heavy bond is B. Note that the ratio of the hydrogen amount can be measured by 1 H-NMR.
- reaction conditions are set so that the value of A / B is in the range of 0 to 0.5, preferably 0 to 0.3. As shown in Examples described later, when the value of A / B exceeds 0.5, there is a possibility that the content of olefin or diene cannot be sufficiently reduced.
- FIG. 2 corresponds to the schematic flow of FIG. 1 (a) and shows a hydrocarbon oil processing apparatus that is attached to the reforming process 3 that uses water during the reforming process.
- the mixed fluid of reformed oil and water flowing out from the reforming process 3 is supplied to the cracking reaction tower 1 via the pump 11 and the heater 12, and is brought into contact with the cracking catalyst and the cracked hydrocarbon oil. Hydrogen is produced.
- the mixed fluid containing these cracked hydrocarbon oil and hydrogen is cooled by the cooler 13 and then free water is separated by the oil / water separator 14.
- the water accumulated in the boot of the oil / water separator 14 is discharged through the cooler 15 and the flow rate control valve 16 and is reused in the reforming process 3, for example.
- the oil / water separation performed in the oil / water separator 14 corresponds to a step of separating water from a mixture of cracked hydrocarbon oil and hydrogen (oil / water separation step).
- the oil / water separation step (oil / water separator 14) may be omitted depending on the necessity.
- the cracked hydrocarbon and hydrogen mixed fluid separated from the free water by the oil / water separator 14 is supplied to the hydrogenation reaction tower 2 through the cooler 21 and the pressure control valve 22, and comes into contact with the hydrogenation catalyst to form olefin, The diene content is reduced. Thereafter, the mixed fluid containing the cracked hydrocarbon, gas generated by the hydrogenation reaction, surplus hydrogen, and the like flows into the oil / water separator 25 through the cooler 23 and the pressure control valve 24.
- the cracked hydrocarbons separated from free water and gas are shipped as synthetic crude oil with reduced olefin and diene contents.
- FIG. 3 corresponds to the schematic flow of FIG. 1 (b), and shows a cracked hydrocarbon oil treatment apparatus provided in the reforming process 3 that does not use water during the reforming process.
- This example is different from the processing apparatus shown in FIG. 2 in that water is mixed with the reformed oil flowing out from the reforming process 3 via the pump 17 and the heater 18.
- FIG. 4 shows a case where the reformed oil that has flowed out of the reforming process 3 is fractionated by a distillation apparatus, and the fraction after fractionation is treated in the decomposition step.
- the mixed fluid of reformed oil and water flowing out from the reforming process 3 and passing through the heater 41 is fractionated into a light fraction and a heavy fraction in the distillation tower 42.
- a mixed fluid of a light fraction and water is processed in the decomposition reaction tower 1.
- olefins and dienes are relatively contained in a fraction at 60 to 220 ° C., so by separating a heavy fraction with a small content of olefins and dienes and then sending it to the cracking process, The load on the decomposition reaction tower 1 can be reduced.
- the distillation column 42 is not limited to the case where the reformed oil is separated into two fractions of a light fraction and a heavy fraction.
- the middle distillate contains a large amount of olefins and dienes
- the reformed oil is separated into three fractions, a light distillate, a middle distillate, and a heavy distillate, and the middle distillate is processed in the cracking process. May be.
- a cooler or the like is provided on the top side of the distillation column 42, but the description thereof is omitted here.
- FIG. 5 shows, as an example of the reforming process 3, a supercritical water reformer that thermally decomposes reformed oil using supercritical water (for example, see Japanese Patent Application Laid-Open No. 2011-88964).
- Raw oil such as ultra-heavy crude oil is supplied to the supercritical water treatment reactor 301 through the pump 302 and the heater 303 at a temperature at which polycondensation does not occur, for example, 300 ° C. to 450 ° C.
- water is supplied to the supercritical water treatment reactor 301 through the pump 304 and the heater 305 at a critical temperature (374 ° C.) or higher, for example, 450 ° C. to 600 ° C.
- the supercritical water treatment reactor 301 has a critical water pressure of 22.1 MPa or more, for example, 25 to 30 MPa, 374 ° C. to 500 ° C., and pyrolysis of the raw material oil in the supercritical water treatment reactor 301 is performed.
- the light oil obtained as a result is extracted into the supercritical water phase and supplied to the cracking reaction tower 1.
- the point which the cracked hydrocarbon oil by which content of the olefin and the diene was reduced through the cracking process and the hydrogenation process turns into a raw material of synthetic crude oil is the same as the example shown in FIG.
- the water separated in each step is recycled again as a raw material for supercritical water through a line provided with a recycle water tank 56 and pumps 57 and 19.
- the decomposition step may be carried out by providing a decomposition catalyst inside the supercritical water reactor 301 without providing the decomposition reaction tower 1.
- heavy oil that has not been extracted into supercritical water is supplied to a flash drum 53 having a pressure condition of about 0.1 to 8 MPa and a temperature condition of about 250 to 430 ° C. via a cooler 51 and a flow control valve 52. Then, water and light oil dissolved in the heavy oil are separated by flash distillation. The flash-distilled water and light oil are separated into water and light oil through a cooler 54 and an oil / water separator 55, and the light oil becomes a raw material for synthetic crude oil, and water is recycled.
- the light oil content may be processed in a cracking step and a hydrogenation step to reduce the content of olefins and dienes.
- a part of the heavy oil separated from the light oil and the like by the flash drum 53 is mixed with synthetic crude oil, while the rest is used as residual oil as fuel for a heating furnace that constitutes the heaters 303 and 305. .
- the reformed oil flowing out from the reforming process provided at the well source is decomposed and hydrogenated.
- An example of processing is given.
- Table 1 shows the properties of the reformed oil used in the experiments described below.
- the ratio of the hydrogen attributed to olefins in the hydrocarbon oil (total olefin H) to the total hydrogen amount was determined by proton NMR analysis (NMR system-500, manufactured by VARIAN).
- NMR system-500 proton NMR analysis
- CGO + LCO indicates a mixed oil of cracked light oil (Coker Gas Oil: CGO) obtained from coker and LCO (Light Cycle Oil) obtained from FCC.
- the supercritical water reformed oil is a reformed oil (corresponding to a light oil component and containing water) reformed by using the supercritical water treatment process exemplified in the supercritical water treatment reactor 301 of FIG.
- Example 1 The CGO + LCO was processed using a test apparatus having the same configuration as the processing apparatus shown in FIG.
- the decomposition catalyst of the decomposition reaction tower 1 includes Zr as the element X, Ce as the element Y 1 , W as the element Y 2 , a value x / (y 1 + y 2 ) of 1, and a value y 2 / y 1 of 0.
- a mixed metal oxide of 0.06 was used.
- Example 1-2 The supercritical water reformed oil was processed using a test apparatus having the same configuration as the processing apparatus shown in FIG.
- the structures of the cracking catalyst and the hydrogenation catalyst are the same as in Example 1-1 (the conditions of the catalyst are the same in the following examples).
- FIG. 6 is a graph showing the hydrogenation reaction temperature on the horizontal axis and the ratio [% H] of the total olefin H to the total hydrogen amount on the vertical axis for the oil after the reaction.
- the total olefin H is calculated by adding the proportion of the hydrogen amount attributed to each of the terminal olefin and the internal olefin.
- the thin broken line indicates the total olefin H in the CGO + LCO before reforming as a baseline, and the thick broken line indicates the total olefin H in the supercritical water reformed oil before treatment as the baseline.
- Example 1-1 CGO + LCO
- Example 1-2 supercritical water reformed oil
- Example 2 A decomposition step and a hydrogenation step were performed on CGO + LCO, and changes in the ratio of terminal olefin H and internal olefin H were examined.
- FIG. 8 shows a diagram plotted against the above.
- the horizontal axis in FIG. 8 indicates the temperature of the hydrogenation reaction
- the vertical axis indicates the value of terminal olefin H / internal olefin H (the same applies in FIG. 11 for the vertical axis and the horizontal axis).
- the change in the value of the terminal olefin H / internal olefin H shown in FIG. 8 shows that the terminal olefin H / internal olefin H increases as the temperature increases under the low temperature condition of 100 to 200 ° C. of the hydrogenation reaction. The value of suddenly decreased. This is because while the internal olefin H remained almost constant, the terminal olefin H decreased dramatically as the temperature increased. Under this temperature condition, the internal olefin was hardly hydrogenated, but the terminal olefin was hydrogenated. It is shown that.
- Example 3 The supercritical water reformed oil was subjected to a cracking process and a hydrogenation process, and changes in the ratio of terminal olefin H and internal olefin H were examined.
- A. Experimental conditions The same supercritical water reforming oil as used in Example 1-2 was used.
- the test apparatus which processed the supercritical water reforming oil is different from the processing apparatus shown in FIG. 2 in that the cooler 13 and the oil / water separator 14 are not provided in the rear stage of the decomposition reaction tower 1.
- FIG. 9 shows the ratio [% H] of the terminal olefin H and the internal olefin H in the product oil after the cracking process and the hydrogenation process are performed on the supercritical water reformed oil with respect to the total hydrogen amount. .
- the ratio of the terminal olefin H is sufficiently reduced in the temperature range of 200 to 300 ° C., and the content of the olefin H can be reduced even when the oil-water separation step is not provided before the hydrogenation step. confirmed.
- Example 4 The supercritical water reformed oil was subjected to a cracking process and a hydrogenation process, and changes in the ratio of terminal olefin H and internal olefin H were examined.
- FIG. 10 shows the ratio [% H] of the terminal olefin H and the internal olefin H in the produced oil after the cracking process and the hydrogenation process are performed on the supercritical water reformed oil.
- the change of terminal olefin H / internal olefin H is shown in FIG. According to FIG. 10, the change of the ratio of the terminal and internal olefin H with respect to the temperature of the hydrogenation reaction is almost the same as in the case of Example 2 shown in FIG. 7 (when the same treatment is performed on CGO + LCO). There was a trend. Further, the terminal olefin H / internal olefin H also showed the same tendency as in Example 2 shown in FIG.
- Example 5 The cracking step and the hydrogenation step are performed on the light fraction obtained by distilling the supercritical water reformed oil with a distillation apparatus (the fraction lighter than the light oil (distillation property: 360 ° C. or less)), and the terminal olefin H, The change in the proportion of internal olefin H was examined.
- A. Experimental conditions (Example 5) The same supercritical water reformed oil as in Example 1-2 was used, and processing was performed using a test apparatus having the same configuration as the processing apparatus shown in FIG. Table 3 shows the ratio of terminal olefin H and internal olefin contained in the light fraction.
- the tendency confirmed in the above examples is the combination of the elements X, Y 1 and Y 2 of the decomposition catalyst, the value of x / (y 1 + y 2 ), y 2 / y 1 , the titanium dioxide in the hydrogenation catalyst. This also applies when the content ratio, type of active metal, etc. are changed. Therefore, the technical scope of the present invention is not limited only to the case where the cracking catalyst and the hydrogenation catalyst used in the above examples are used.
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Abstract
Description
ジエンおよびオレフィンの少なくとも一方を含有する炭化水素油と水とを温度375~550℃にて分解触媒に接触させて分解し、分解炭化水素油と水素を製造する工程と、
次いで、前記水素と、前記分解炭化水素油とを温度100~374℃にて水素化触媒に接触させ、前記分解炭化水素油の水素化反応を行い、ジエン及びオレフィンの少なくとも一方の含有量を低減する工程と、を有することを特徴とする。
(1)前記分解触媒と接触させた後の分解炭化水素油と水とを含む混合物から、水を分離する工程を有し、水を分離した後の分解炭化水素油に対して水素化反応を行うこと。
(2)前記炭化水素油は、水を用いて原料油を改質して得た改質油を含み、前記分解触媒により水素を生成する水は、当該改質油と共に排出された水であること。また、前記炭化水素油は、超臨界水に原料油を接触させて、得た改質油を含むこと。さらに、前記炭化水素油は、改質油を蒸留して沸点範囲の異なる複数の留分に分離して得た少なくとも1つの留分を含むこと。
(3)前記水素化反応は、前記水素化反応後の分解炭化水素油中の水素量に対する前記ジエン及びオレフィンの末端にある炭素-炭素二重結合の水素量の割合をA、内部にある前記二重結合の水素量の割合をBとしたとき、A/Bの値が0~0.5の範囲となるように行われること。
(4)前記分解触媒は、
(a)IVA族元素から選択される1種の元素Xと、
(b)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y1(但し、元素Xとは異なる元素である。)と、
(c)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y2(但し、元素Xおよび元素Y1とは異なる元素である。)と、を含有し、
(d)元素Y1の存在量y1と元素Y2の存在量y2との合計(y1+y2)に対する元素Xの存在量xの比が、0.5以上2.0以下となり、
(e)元素Y1の存在量y1に対する元素Y2の存在量y2の比が、0.02以上0.25以下となる、比率である複合金属酸化物であること。
例えば、前記元素XがZr、元素Y1がCe、元素Y2がW、FeまたはMnからなるY2元素群から選択された元素であること。
(5)前記水素化触媒は、アルミナおよびシリカを含まない金属酸化物からなる担体に、水素化活性を有する金属を担持したものであること。例えば前記水素化触媒は、ジルコニアまたはアナターゼ型チタニアを含む担体に、ニッケル、コバルトまたはモリブデンからなる群から選択された一種以上の金属を担持したものであること。
ジエンおよびオレフィンの少なくとも一方を含有する炭化水素油と、水とが供給され、当該炭化水素油及び当該水から分解炭化水素油及び水素を生成する分解触媒が充填された分解反応塔と、
前記分解反応塔にて製造された水素と、当該分解反応塔から流出した分解炭化水素油とが供給され、前記分解炭化水素油の水素化反応を進行させて、ジエン及びオレフィンの少なくとも一方の含有量を低減する水素化触媒が充填された水素化反応塔と、を備えたことを特徴とする。
(6)前記分解反応塔から流出した分解炭化水素油と水とを含む混合物から、水を分離する油水分離槽を備え、前記水素化反応塔には、当該油水分離槽にて水が分離された後の分解炭化水素油が供給されること。
(7)前記炭化水素油は、水を用いて原料油を改質する改質装置から得た改質油を含み、前記分解触媒により水素を生成する水は、当該改質油と共に排出された水であること。また、前記炭化水素油は、超臨界水を原料油と接触させて改質する超臨界水改質装置から得た改質油を含むこと。さらに、前記炭化水素油は、改質油を蒸留して沸点範囲の異なる複数の留分に分離する蒸留装置から得た少なくとも1つの留分を含むこと
(8)前記水素化反応は、前記水素化反応後の分解炭化水素油中の水素量に対する前記ジエン及びオレフィンの末端にある炭素-炭素二重結合の水素量の割合をA、内部にある前記二重結合の水素量の割合をBとしたとき、A/Bの値が0~0.5の範囲となるように行われること。
(9)前記分解触媒は、
(a)IVA族元素から選択される1種の元素Xと、
(b)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y1(但し、元素Xとは異なる元素である。)と、
(c)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y2(但し、元素Xおよび元素Y1とは異なる元素である。)と、を含有し、
(d)元素Y1の存在量y1と元素Y2の存在量y2との合計(y1+y2)に対する元素Xの存在量xの比が、0.5以上2.0以下となり、
(e)元素Y1の存在量y1に対する元素Y2の存在量y2の比が、0.02以上0.25以下となる、比率である複合金属酸化物であること。
(10)前記水素化触媒は、アルミナおよびシリカを含まない金属酸化物からなる担体に、水素化活性を有する金属を担持したものであること。
本発明の実施の形態は、炭化水素の分子構造中に、1個の炭素-炭素二重結合(以下、単に二重結合という)を含むオレフィン、または2個の二重結合を含むジエンの少なくとも一方を含有する炭化水素油に適用される。炭化水素は、鎖状炭化水素であってもよいし、ナフテン系炭化水素や芳香族系炭化水素であってもよい。鎖状炭化水素の場合には、炭素骨格中に二重結合を有していてもよいし、側鎖中に二重結合を有していてもよい。また、ナフテン系炭化水素や芳香族系炭化水素の場合には、ナフテン環や芳香族環及びこれらの縮合環に結合した側鎖中の二重結合が処理対象となる。これらの炭化水素中には、酸素や窒素、硫黄などの原子が含まれていてもよい。なお、本発明では二重結合を1個または2個含む比較的低分子の炭化水素に着目し、当該二重結合の低減を図っているが、本処理の適用に伴って3個以上の二重結合を含む炭化水素中の二重結合の含有量が低減されてもよいことは勿論である。
そこで本発明者らは、井戸元などでも容易に入手できる水を用いて改質油との触媒反応により水素を発生させ、その水素を用いて水素化反応により当該改質油中のオレフィンやジエンを低減する技術を開発するに至った。
図1(a)、(b)は、実施の形態に係るプロセスの概略フロー図を示している。本図によれば、改質プロセス3から流出し、オレフィンやジエンを含む改質油と水とが分解反応塔1に供給され、分解触媒と接触して分解炭化水素油及び水素が製造される(分解工程)。これらの分解炭化水素油及び水素は水素化反応塔2に供給され、水素化触媒と接触して水素化反応によりオレフィン、ジエンの含有量が低減される(水素化工程)。水素化反応塔2から得られたオレフィン、ジエンの含有量の低い分解炭化水素油は、合成原油の原料などとなる。
分解反応塔1には分解触媒が充填され、水素化反応塔2には水素化触媒が充填されているが、各触媒と改質油や分解炭化水素油とを接触させる手法は、固定床にこれらの流体を通流させる場合に限らず、流動床式や沸騰床式など好適な手法を採用してよい。
(反応)
分解工程においては改質油と水とを分解触媒に接触させてこれら改質油及び水を分解し、分解炭化水素油と水素とを得る。改質油及び水を分解する反応としては、例えば分解触媒中に含まれる酸化物中の格子酸素を利用して改質油を分解する一方、当該分解触媒中に水分解触媒を含有させることで水を分解し、格子欠陥中に酸素を補充する。この水分解によって水素が発生し、これら分解炭化水素と水素とが水素化工程へと送られる。
上述の反応を進行させる分解触媒としては、例えば、2種以上の金属酸化物が複合して生ずる酸化物である複合金属酸化物を用いることができる。具体的には、所定の元素X、Y1およびY2を含む複合金属酸化物を分解触媒として用いることができる。分解触媒として用いる複合金属酸化物の結晶構造は、例えばX線回折分析を用いて評価することができる。
(a)IVA族元素から選択される1種の元素Xと、
(b)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y1(但し、元素Xとは異なる元素である。)と、
(c)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y2(但し、元素Xおよび元素Y1とは異なる元素である。)と、
の3種の金属元素を所定の比率で含有している複合金属酸化物を挙げることができる。
(d)元素Y1の存在量y1と元素Y2の存在量y2との合計(y1+y2)に対する元素Xの存在量xの比が、0.5以上2.0以下(0.5≦x/(y1+y2)≦2.0)となり、
(e)元素Y1の存在量y1に対する元素Y2の存在量y2の比が、0.02以上0.25以下(0.02≦y2/y1≦0.25)となる、比率を挙げることができる。
(i)まず、複合金属酸化物を構成する金属元素を含む水溶液を調製する。
(ii)次に、調製した水溶液に対し、アンモニア水や、炭酸ナトリウム水溶液などの共沈剤を、水溶液のpHがアルカリ側に偏らないように(例えばpHが5~8の範囲となるように)調整しながら滴下し、共沈殿物を生成させる。
(iii)そして最後に、得られた沈殿をろ過および乾燥した後、乾燥した沈殿を焼成して複合金属酸化物とする。
ここで、上記(iii)において沈殿を乾燥する温度は、水分を効率的に蒸発させる観点からは100℃以上であることが好ましく、急激な乾燥を防止する観点からは160℃以下であることが好ましい。また、乾燥した沈殿を焼成する温度は、生成する複合金属酸化物(触媒)の構造安定性(即ち、触媒として使用して炭化水素油を分解した際の複合金属酸化物の構造変化の抑制)の観点からは500℃以上であることが好ましく、生成する複合金属酸化物の表面積の減少を抑制する観点からは900℃以下であることが好ましい。
上記分解触媒を用いた分解工程は、例えば375~550℃の温度条件下で行われ、好ましくは390~500℃、の温度条件が選択される。温度が375℃未満の場合、水が超臨界状態とならず、また、反応に必要な活性化エネルギーが得られず十分な水素が得られないおそれがある一方、550℃超の温度条件下では、必要以上の水素が発生するばかりでなく熱分解の進行により改質油がガス化して液収率が低下したり、発生した水素が再消費されたりするおそれがある。また、熱分解によってオレフィン、ジエンの含有量の増加も懸念される。
(反応)
水素化工程においては、分解炭化水素油と水素とを水素化触媒に接触させて分解炭化水素油を水素化し、二重結合を開裂させてオレフィンやジエンの含有量を低減する。
ここで、当該水素化工程の上流側の分解工程においては、水を用いて分解炭化水素油と水素とが製造されているため、分解炭化水素油中に水分が含まれている場合がある。そこで上述の水素化反応を進行させる水素化触媒としては、高温高圧の水蒸気により触媒の結晶構造が大きく変化して触媒が使用不能となるアルミナ(特にγ-アルミナ)やシリカを含まない金属酸化物からなる担体に、水素化活性を有する金属を担持したものを用いることが好ましい。
なお、分解工程と水素化工程との間に、分解炭化水素油中の水分を除去する工程を設け、当該炭化水素油中の水分を低減できる場合には、担体としてγ-アルミナやシリカを含む担体に前記活性金属を担持した水素化触媒を用いてもよい。
上記水素化触媒を用いた水素化工程は、例えば100~374℃の温度条件下で行われ、好ましくは200~350℃の温度条件が選択される。温度が100℃未満の場合、反応に必要な活性化エネルギーが得られずオレフィンやジエンの含有量を十分に低減できないおそれがある一方、374℃超の温度条件下では、水素化反応と同時に熱分解が進行し、分解炭化水素油がガス化して液収率が低下するおそれがある。
ここでオレフィンやジエンの分子構造に着目したとき、炭素骨格や側鎖の末端に位置する二重結合は、当該末端よりも内部側に位置する二重結合と比較して、より穏やかな条件(低温、低圧、低水素/油比)下で水素化反応を進行させることができる。そこで、この分子構造の観点から水素化反応の条件を調節し、予め設定されている目標値を満足しつつ、できるだけ穏やかな条件下で水素化反応を進行させることができれば、ガスの発生を抑え液収率の高い反応条件を探索することも可能となる。
次に、図2~図5を参照しながら実施の形態に関わる処理装置の構成例を説明する。なお、これらの図において各処理装置に共通の設備には、共通の符号を付してある。
図2は、図1(a)の概略フローに対応し、改質処理の際に水を利用する改質プロセス3に併設される炭化水素油の処理装置を示している。この例では、改質プロセス3から流出した改質油と水との混合流体が、ポンプ11、加熱器12を介して分解反応塔1に供給され、分解触媒と接触して分解炭化水素油と水素とが製造される。
また、図4に示した蒸留装置において、蒸留塔42の塔頂側には冷却器などが設けられているが、ここではその記載を省略してある。
超重質原油などの原料油は、ポンプ302、加熱器303を介し、重縮合が発生しない程度の例えば300℃~450℃で超臨界水処理反応器301に供給される。一方、水は、ポンプ304、加熱器305を介し、臨界温度(374℃)以上の例えば450℃~600℃で超臨界水処理反応器301に供給される。
フラッシュドラム53にて軽質油分等と分離された重質油分は、その一部は合成原油に混合される一方、残りは残渣油として加熱器303、305を成す加熱炉の燃料などとして利用される。
以下に説明する実験にて使用した改質油の性状を表1に示す。炭化水素油中のオレフィンに帰属する水素(全オレフィンH)の全水素量に対する割合の定量は、プロトンNMR分析(VARIAN社製 NMR system-500)により行った。ここで、当該全オレフィンHのうち、炭素骨格や側鎖の最末端に位置する炭素に結合している水素(末端オレフィンH)、及び当該末端の炭素よりも内側の炭素に結合している水素(内部オレフィンH)はNMRピークの位置に基づき区別した。
表1中、CGO+LCOは、コーカーから得られた分解軽油(Coker Gas Oil:CGO)とFCCから得られたLCO(Light Cycle Oil)との混合油を示す。また、超臨界水改質油は図5の超臨界水処理反応器301に例示した超臨界水処理プロセスを用いて改質した改質油(軽質油分に相当し、水を含む)を示す。
水素化工程によって改質油中の全オレフィンHがどの程度削減されるかを調べた。
A.実験条件
表2に示す性状を有する改質油に対し、分解工程、水素化工程で処理を行い、全オレフィンHの変化を調べた。
(実施例1-1)
CGO+LCOに対し、図3に示した処理装置と同様の構成を有する試験装置を用いて処理を行った。分解反応塔1の分解触媒は、元素XとしてZr、元素Y1としてCe、元素Y2としてWを含み、x/(y1+y2)の値が1、y2/y1の値が0.06の複合金属酸化物を用いた。また、水素化反応塔2の水素化触媒は、アナターゼ型の二酸化チタンが100質量%の担体に、活性金属としてNi‐Moを担持したものを用いた。
(実施例1-2)
超臨界水改質油に対しては、図2に示した処理装置と同様の構成を有する試験装置を用いて処理を行った。分解触媒、水素化触媒の構成は実施例1-1と同様である(触媒の条件については以下の各実施例で同じ)。
原料油流量:50ml/hr、
(a)分解反応
温度:430℃、圧力:25MPaG、水/油比:1.58(重量比)
(b)水素化反応
温度:100、150、200、250、300、350℃、圧力:5MPaG
反応後の油について、水素化反応の温度を横軸、全オレフィンHの全水素量に対する割合[%H]を縦軸にしたグラフを図6に示す。ここでは、末端オレフィン、内部オレフィンそれぞれに帰属した水素量の割合を足し、全オレフィンHを算出している。また、細い破線は改質前のCGO+LCO中の全オレフィンHをベースラインとして示し、太い破線は処理前の超臨界水改質油中の全オレフィンHをベースラインとして示した。実施例1-1(CGO+LCO)、実施例1-2(超臨界水改質油)共に、水素化温度が高くなるに従い、全オレフィンHが減少した。水素化工程によりオレフィンHの含有量が低減されていることが分かる。
CGO+LCOに対し分解工程及び水素化工程を実施し、末端オレフィンH、内部オレフィンHの割合の変化を調べた。
A.実験条件
(実施例2)
実施例1-1と同様のCGO+LCO及び試験装置を用いて処理を行った。
<反応条件>
原料油流量:50ml/hr
(a)分解反応
温度:430℃、圧力:25MPaG、水/油比:1.58(重量比)
(b)水素化反応
温度:100、150、200、250、300、350℃、圧力:5MPaG
CGO+LCOに対して分解工程、水素化工程を実施した後の分解炭化水素油(簡便のため、以下、生成油という)中の末端オレフィンHおよび内部オレフィンHの全水素量に対する割合[%H]を図7に示す。図7の横軸は、水素化反応の温度を示し、縦軸は末端、内部オレフィンHの割合を示す。同図中、末端オレフィンH(特許請求の範囲における「水素量の割合A」に相当する)は、ひし形のプロット、内部オレフィンH(同じく「水素量の割合B」に相当する)は三角のプロットで示してある。また、図中の細い破線は改質前のCGO+LCO中の末端オレフィンHをベースラインとして示し、太い破線は改質前の同油中の内部オレフィンHをベースラインとして示した(縦軸、横軸や凡例につき、図9、図10、図12において同じ)。
また、得られた末端オレフィンH、内部オレフィンHの割合より、末端オレフィンH/内部オレフィンH(特許請求の範囲の「A/B」の値に相当する)を算出し、水素化反応の温度に対してプロットした図を図8に示す。図8の横軸は、水素化反応の温度を示し、縦軸は末端オレフィンH/内部オレフィンHの値を示す(縦軸、横軸につき、図11において同じ)。
超臨界水改質油に対し分解工程及び水素化工程を実施し、末端オレフィンH、内部オレフィンHの割合の変化を調べた。
A.実験条件
(実施例3)
実施例1-2と同様の超臨界水改質油を用いた。また、当該超臨界水改質油の処理を行った試験装置には分解反応塔1の後段の冷却器13、油水セパレーター14が設けられていない点が図2に示す処理装置と異なる。
<反応条件>
原料油流量:50ml/hr
(a)水分解反応
温度:430℃、圧力:25MPaG、水/油比:1.58(重量比)
(b)水素化反応
温度:200、250、300℃、圧力:5MPaG
超臨界水改質油に対して分解工程、水素化工程を実施した後の生成油中の末端オレフィンHおよび内部オレフィンHの全水素量に対する割合[%H]を図9に示す。
図9によれば200~300℃の温度範囲で末端オレフィンHの割合が十分に低下しており、水素化工程の前に油水分離工程を設けない場合でも、オレフィンHの含有量を低減できることが確認された。
超臨界水改質油に対し分解工程及び水素化工程を実施し、末端オレフィンH、内部オレフィンHの割合の変化を調べた。
A.実験条件
(実施例4)
実施例1-2と同様の超臨界水改質油及び試験装置を用いて処理を行った。
<反応条件>
原料油流量:50ml/hr
(a)分解反応
温度:430℃、圧力:25MPaG、水/油比:1.58(重量比)
(b)水素化反応
温度:100、150、200、250、300、350℃、圧力:5MPaG
超臨界水改質油に対して分解工程、水素化工程を実施した後の生成油中の末端オレフィンHおよび内部オレフィンHの全水素量に対する割合[%H]を図10に示し、末端オレフィンH/内部オレフィンHの変化を図11に示す。
図10によれば、水素化反応の温度に対する末端、内部オレフィンHの割合の変化は、図7に示した実施例2の場合(CGO+LCOに対して同様の処理を行った場合)とほぼ同様の傾向がみられた。また、末端オレフィンH/内部オレフィンHについても図8に示した実施例2と同様の傾向を示した。
超臨界水改質油を蒸留装置で蒸留して得た軽質留分(軽油より軽質な留分(蒸留性状360℃以下))に対して分解工程及び水素化工程を実施し、末端オレフィンH、内部オレフィンHの割合の変化を調べた。
A.実験条件
(実施例5)
実施例1-2と同様の超臨界水改質油を用い、図4に示した処理装置と同様の構成を有する試験装置を用いて処理を行った。
軽質留分中に含まれる末端オレフィンH、内部オレフィンの割合を表3に示す。
原料油流量:50ml/hr
(a)分解反応
温度:430℃、圧力:25MPaG、水/油比:1.58(重量比)
(b)水素化反応
温度:200、250、300℃、圧力:5MPaG
超臨界水改質油を蒸留して得た軽質留分に対して分解工程、水素化工程を実施した後の生成油中の末端オレフィンHおよび内部オレフィンHの全水素量に対する割合[%H]を図12に示す。
図12によれば、超臨界水改質油を蒸留して得た軽質留分を原料とした時も、オレフィンHの含有量の低下が確認された。改質プロセスの後に蒸留を行って得られた留分の一部に対して分解工程や水素化工程を実施することにより、改質プロセスに処理可能な原料油の増加や触媒使用量の低減が可能となる。
以上の実施例で確認された傾向は、分解触媒の元素X、Y1、Y2の組み合わせやx/(y1+y2)、y2/y1の値、水素化触媒中の二酸化チタンの含有割合、活性金属の種類等を変更した場合にも当てはまる。従って、本発明の技術的範囲は、上記実施例にて用いた分解触媒、水素化触媒を用いる場合のみに限定されるものではない。
14 油水セパレーター
2 水素化反応塔
3 改質プロセス
301 超臨界水処理反応器
42 蒸留塔
Claims (18)
- 炭化水素油の処理方法において、
ジエンおよびオレフィンの少なくとも一方を含有する炭化水素油と水とを温度375~550℃にて分解触媒に接触させて分解し、分解炭化水素油と水素を製造する工程と、
次いで、前記水素と、前記分解炭化水素油とを温度100~374℃にて水素化触媒に接触させ、前記分解炭化水素油の水素化反応を行い、ジエン及びオレフィンの少なくとも一方の含有量を低減する工程と、を有することを特徴とする炭化水素油の処理方法。 - 前記分解触媒と接触させた後の分解炭化水素油と水とを含む混合物から、水を分離する工程を有し、水を分離した後の分解炭化水素油に対して水素化反応を行うことを特徴とする請求項1に記載の炭化水素油の処理方法。
- 前記炭化水素油は、水を用いて原料油を改質して得た改質油を含み、前記分解触媒により水素を生成する水は、当該改質油と共に排出された水であることを特徴とする請求項1または2に記載の炭化水素油の処理方法。
- 前記炭化水素油は、超臨界水に原料油を接触させて、得た改質油を含むことを特徴とする請求項1乃至3の何れかに記載の炭化水素油の処理方法。
- 前記炭化水素油は、改質油を蒸留して沸点範囲の異なる複数の留分に分離して得た少なくとも1つの留分を含むことを特徴とする請求項3または4に記載の炭化水素油の処理方法。
- 前記水素化反応は、前記水素化反応後の分解炭化水素油中の水素量に対する前記ジエン及びオレフィンの末端にある炭素-炭素二重結合の水素量の割合をA、内部にある前記二重結合の水素量の割合をBとしたとき、A/Bの値が0~0.5の範囲となるように行われることを特徴とする請求項1乃至5の何れかに記載の炭化水素油の処理方法。
- 前記分解触媒は、
(a)IVA族元素から選択される1種の元素Xと、
(b)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y1(但し、元素Xとは異なる元素である。)と、
(c)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y2(但し、元素Xおよび元素Y1とは異なる元素である。)と、を含有し、
(d)元素Y1の存在量y1と元素Y2の存在量y2との合計(y1+y2)に対する元素Xの存在量xの比が、0.5以上2.0以下となり、
(e)元素Y1の存在量y1に対する元素Y2の存在量y2の比が、0.02以上0.25以下となる、比率である複合金属酸化物であることを特徴とする請求項1乃至6の何れかに記載の炭化水素油の処理方法。 - 前記元素XがZr、元素Y1がCe、元素Y2がW、FeまたはMnからなるY2元素群から選択された元素であることを特徴とする請求項7に記載の炭化水素油の処理方法。
- 前記水素化触媒は、アルミナおよびシリカを含まない金属酸化物からなる担体に、水素化活性を有する金属を担持したものであることを特徴とする請求項1乃至8の何れかに記載の炭化水素油の処理方法。
- 前記水素化触媒は、ジルコニアまたはアナターゼ型チタニアを含む担体に、ニッケル、コバルトまたはモリブデンからなる群から選択された一種以上の金属を担持したものであることを特徴とする請求項9に記載の炭化水素油の処理方法。
- 炭化水素油の処理装置において、
ジエンおよびオレフィンの少なくとも一方を含有する炭化水素油と、水とが供給され、当該炭化水素油及び当該水から分解炭化水素油及び水素を生成する分解触媒が充填された分解反応塔と、
前記分解反応塔にて製造された水素と、当該分解反応塔から流出した分解炭化水素油とが供給され、前記分解炭化水素油の水素化反応を進行させて、ジエン及びオレフィンの少なくとも一方の含有量を低減する水素化触媒が充填された水素化反応塔と、を備えたことを特徴とする炭化水素油の処理装置。 - 前記分解反応塔から流出した分解炭化水素油と水とを含む混合物から、水を分離する油水分離槽を備え、前記水素化反応塔には、当該油水分離槽にて水が分離された後の分解炭化水素油が供給されることを特徴とする請求項11に記載の炭化水素油の処理装置。
- 前記炭化水素油は、水を用いて原料油を改質する改質装置から得た改質油を含み、前記分解触媒により水素を生成する水は、当該改質油と共に排出された水であることを特徴とする請求項11または12に記載の炭化水素油の処理装置。
- 前記炭化水素油は、超臨界水を原料油と接触させて改質する超臨界水改質装置から得た改質油を含むことを特徴とする請求項11乃至13の何れかに記載の炭化水素油の処理装置。
- 前記炭化水素油は、改質油を蒸留して沸点範囲の異なる複数の留分に分離する蒸留装置から得た少なくとも1つの留分を含むことを特徴とする請求項13または14に記載の炭化水素油の処理装置。
- 前記水素化反応は、前記水素化反応後の分解炭化水素油中の水素量に対する前記ジエン及びオレフィンの末端にある炭素-炭素二重結合の水素量の割合をA、内部にある前記二重結合の水素量の割合をBとしたとき、A/Bの値が0~0.5の範囲となるように行われることを特徴とする請求項11乃至15の何れかに記載の炭化水素油の処理装置。
- 前記分解触媒は、
(a)IVA族元素から選択される1種の元素Xと、
(b)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y1(但し、元素Xとは異なる元素である。)と、
(c)IIIA族元素、VIA族元素およびVIIA族元素、並びに、第4~6周期のIVA族元素および第4周期のVIII族元素からなる群より選択される1種の元素Y2(但し、元素Xおよび元素Y1とは異なる元素である。)と、を含有し、
(d)元素Y1の存在量y1と元素Y2の存在量y2との合計(y1+y2)に対する元素Xの存在量xの比が、0.5以上2.0以下となり、
(e)元素Y1の存在量y1に対する元素Y2の存在量y2の比が、0.02以上0.25以下となる、比率である複合金属酸化物であることを特徴とする請求項11乃至16の何れかに記載の炭化水素油の処理装置。 - 前記水素化触媒は、アルミナおよびシリカを含まない金属酸化物からなる担体に、水素化活性を有する金属を担持したものであることを特徴とする請求項11乃至17の何れかに記載の炭化水素油の処理装置。
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CA (1) | CA2883104C (ja) |
CO (1) | CO7270467A2 (ja) |
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CN108472611B (zh) * | 2015-12-15 | 2021-11-30 | 沙特阿拉伯石油公司 | 用于石油升级的超临界反应器系统和工艺 |
US11566186B2 (en) | 2018-05-15 | 2023-01-31 | Worcester Polytechnic Institute | Water-assisted zeolite upgrading of oils |
Citations (4)
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JP2002155286A (ja) * | 2000-11-20 | 2002-05-28 | Mitsubishi Materials Corp | 重質炭素資源の改質方法 |
JP2009242467A (ja) * | 2008-03-28 | 2009-10-22 | Japan Energy Corp | 炭化水素油の分解方法 |
JP2011504966A (ja) * | 2007-11-28 | 2011-02-17 | サウジ アラビアン オイル カンパニー | 水素の供給を用いない重質及び高ワックス質原油のアップグレード法 |
WO2012037011A1 (en) * | 2010-09-14 | 2012-03-22 | Saudi Arabian Oil Company | Sulfur removal from heavy hydrocarbon feedstocks by supercritical water treatment followed by hydrogenation |
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US6315890B1 (en) * | 1998-05-05 | 2001-11-13 | Exxonmobil Chemical Patents Inc. | Naphtha cracking and hydroprocessing process for low emissions, high octane fuels |
BRPI0923010A2 (pt) * | 2008-12-18 | 2015-12-15 | Uop Llc | processo e aparelho para melhorar as propriedades de fluxo de petróleo cru |
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- 2013-09-17 CA CA2883104A patent/CA2883104C/en not_active Expired - Fee Related
- 2013-09-17 WO PCT/JP2013/005475 patent/WO2014054234A1/ja active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002155286A (ja) * | 2000-11-20 | 2002-05-28 | Mitsubishi Materials Corp | 重質炭素資源の改質方法 |
JP2011504966A (ja) * | 2007-11-28 | 2011-02-17 | サウジ アラビアン オイル カンパニー | 水素の供給を用いない重質及び高ワックス質原油のアップグレード法 |
JP2009242467A (ja) * | 2008-03-28 | 2009-10-22 | Japan Energy Corp | 炭化水素油の分解方法 |
WO2012037011A1 (en) * | 2010-09-14 | 2012-03-22 | Saudi Arabian Oil Company | Sulfur removal from heavy hydrocarbon feedstocks by supercritical water treatment followed by hydrogenation |
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RU2617846C2 (ru) | 2017-04-28 |
RU2015115923A (ru) | 2016-11-27 |
JP2014074111A (ja) | 2014-04-24 |
CO7270467A2 (es) | 2015-05-19 |
CA2883104C (en) | 2017-06-27 |
CA2883104A1 (en) | 2014-04-10 |
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