WO2015098754A1 - 石油コークス及びその製造方法 - Google Patents
石油コークス及びその製造方法 Download PDFInfo
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- WO2015098754A1 WO2015098754A1 PCT/JP2014/083718 JP2014083718W WO2015098754A1 WO 2015098754 A1 WO2015098754 A1 WO 2015098754A1 JP 2014083718 W JP2014083718 W JP 2014083718W WO 2015098754 A1 WO2015098754 A1 WO 2015098754A1
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- petroleum coke
- fluid catalytic
- catalytic cracking
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/045—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing mineral oils, bitumen, tar or the like or mixtures thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
Definitions
- the present invention relates to petroleum coke and a method for producing the same.
- Needle coke is generally manufactured using heavy oils such as petroleum heavy oil and coal tar as raw materials, and is used as an aggregate for graphite electrodes for electric steelmaking.
- needle coke having a predetermined particle size is mixed with a binder pitch at a predetermined ratio, and then extruded, fired, and graphitized.
- Graphitization is a process of heat treatment at about 3000 ° C., and a method using a direct energization type furnace (LWG furnace) is common.
- LWG furnace direct energization type furnace
- the graphite electrode is used under severe conditions such as a high temperature atmosphere, it is desired that the coefficient of thermal expansion (CTE) is low. That is, the smaller the CTE, the smaller the electrode consumption during electric steelmaking, and the cost of electric steelmaking can be reduced. In order to reduce the CTE of the graphite electrode, it is necessary to reduce the CTE of the needle coke.
- CTE coefficient of thermal expansion
- Patent Document 1 describes that a bottom oil of a residual oil fluid catalytic cracker (RFCC) and a residual oil under reduced pressure are mixed and subjected to delayed coking.
- Patent Document 2 includes a first heavy oil obtained by hydrodesulfurizing heavy oil under a total pressure of 16 MPa or more, and a second heavy oil derived from a residual oil fluid catalytic cracker (RFCC). Mixing and delayed coking are described.
- Patent Document 3 describes that a first heavy oil obtained as a vacuum distillation residue oil and a second heavy oil derived from a residual fluid fluid catalytic cracker (RFCC) are mixed and subjected to delayed coking. Yes.
- Needle coke is a process in which high temperature treatment of heavy oil causes pyrolysis and polycondensation reactions to produce liquid crystal spheres called mesophase, which combine to produce large liquid crystals called bulk mesophase as intermediate products. It is manufactured through.
- bottom oil of a fluid catalytic cracker residual oil obtained by distilling low sulfur crude oil under reduced pressure, and heavy oil with high sulfur content Any of heavy oils subjected to advanced hydrodesulfurization treatment or mixtures thereof are used.
- the petrochemical industry has demanded a lot of petrochemical raw materials, and it has been required to obtain petrochemical raw materials such as propylene instead of gasoline as much as possible, and high catalytic cracking operation is required in fluid catalytic cracking equipment. . Therefore, the obtained fluid catalytic cracking residual oil has a high sulfur content and nitrogen content as a high cracking fluid catalytic cracking residual oil. In this case, low puffing needle coke may not be obtained.
- This invention is made
- CTE Thermal expansion coefficient
- a light oil having a final boiling point of 380 ° C. or lower, an initial boiling point of 200 ° C. or higher, an aroma component of 50% by mass or higher, and a sulfur content of 0.1% is provided.
- a method for producing petroleum coke which comprises a step of coking a feed oil containing at least 5% by mass and a heavy oil having a nitrogen content of 0.2% by mass or less.
- the petroleum coke obtained by the manufacturing method of the said petroleum coke is provided.
- the inventors focused on the fact that the residual oil has a high sulfur content, while the coke yield when coking is low and the sulfur content in the coke is concentrated at a high concentration, so that the puffing increases. Therefore, the present inventors have intensively studied, and by interposing light oil that does not coking in the coking reaction of heavy oil, gas generation derived from residual oil is expressed by light oil, and sulfur content is reduced. I found it. Heavy oil alone forms a good bulk mesophase, and light oil-derived gas plays the role of appropriate gas generation during solidification. As a result, it is possible to obtain petroleum coke in which CTE is sufficiently small and puffing is sufficiently suppressed.
- the heavy oil and light oil used in the present invention will be described.
- the initial boiling point of the heavy oil used in the present invention is 200 ° C. or higher, preferably 250 ° C. or higher.
- a preferred upper limit is 300 ° C.
- the aroma component of the heavy oil used in the present invention is 50% by mass or more, and preferably 70% by mass or more.
- a preferable upper limit is 90% by mass. This is because, within such a range, a good bulk mesophase is formed and the progress of the coking reaction is promoted.
- the sulfur content of the heavy oil used in the present invention is 0.5% by mass or less, preferably 0.4% by mass or less, and more preferably 0.3% by mass or less.
- a preferred lower limit is 0.1% by mass. This is because when the sulfur content exceeds 0.5% by mass, puffing of petroleum coke cannot be sufficiently suppressed.
- the sulfur content is measured based on the method described in JIS M 8813-Appendix 2: 2006.
- the heavy oil used in the present invention has a nitrogen content of 0.2% by mass or less, preferably 0.15% by mass or less, and more preferably 0.10% by mass or less.
- a preferable lower limit is 0.01% by mass. This is because if the nitrogen content exceeds 0.2% by mass, puffing of petroleum coke cannot be sufficiently suppressed.
- the nitrogen content is measured based on the method described in JIS M 8813-Appendix 4: 2006.
- two or more heavy oils may be used in combination.
- the heavy oil used in the present invention can be obtained by, for example, fluid catalytic cracking, and is particularly limited as long as it is a heavy oil satisfying the above-mentioned conditions in terms of initial boiling point, aroma component, sulfur content and nitrogen content.
- it is preferably a hydrocarbon oil having a density at 15 ° C. of 0.8 g / cm 3 or more.
- the density is a value measured based on the method described in JIS K 2249-1: 2011.
- Examples of such heavy oil feedstocks include atmospheric distillation residue, vacuum distillation residue, shale oil, tar sand bitumen, orinocotal, coal liquefied oil, and heavy oil obtained by hydrorefining these. It is done.
- such heavy oil feedstock may contain relatively light oil such as straight-run gas oil, vacuum gas oil, desulfurized gas oil, desulfurized vacuum gas oil, and preferably vacuum gas oil.
- the vacuum gas oil is a desulfurized vacuum gas oil obtained by subjecting the atmospheric distillation residue oil to vacuum distillation and directly desulfurizing the resulting vacuum gas oil (preferably having a sulfur content of 500 mass ppm or less and a density of 0.1 at 15 ° C. 8 / cm 3 or more).
- Atmospheric distillation residue is obtained by subjecting crude oil to an atmospheric distillation device, for example, heating under normal pressure, and depending on the boiling point of the contained fraction, gas / LPG, gasoline fraction, kerosene fraction, light oil fraction, ordinary oil fraction, One of the fractions obtained when divided into pressure residue oils, the fraction with the highest boiling point.
- the heating temperature varies depending on the production area of the crude oil and is not limited as long as it can be fractionated into these fractions.
- the crude oil is heated to 320 ° C.
- Vacuum distillation residue (VR) is obtained by subjecting crude oil to an atmospheric distillation apparatus to obtain gas, light oil, and atmospheric residue oil. Then, the atmospheric residue oil is removed from the heating furnace at a reduced pressure of 10 to 30 Torr, for example. This is a bottom oil of a vacuum distillation apparatus obtained by changing the temperature in the range of 320 to 360 ° C.
- the conditions for fluid catalytic cracking are not particularly limited as long as it is possible to obtain a heavy oil whose initial boiling point, aroma component, sulfur content and nitrogen content satisfy the above-mentioned conditions.
- the total pressure is 1 to 3 kg / cm 2 G
- the ratio of catalyst to oil (catalyst / oil) is 1 to 20
- the contact time is 1 to 10 seconds.
- the catalyst used for fluid catalytic cracking include a zeolite catalyst, a silica alumina catalyst, or a catalyst in which a noble metal such as platinum is supported on these catalysts.
- the light oil used in the present invention is preferably a light oil having a high aromatic content.
- a typical example of such light oil is coker light oil. This is because such a light oil has high aromaticity and is excellent in compatibility with heavy oil. When the compatibility is improved, the light oil is uniformly dispersed in the heavy oil, so that gas generation occurs uniformly, and the acicularity of coke tends to develop. As a result, the CTE of coke decreases.
- the process used in order to obtain this light oil is not specifically limited. Examples thereof include a delayed coking process, a visbreaking process, a yurika process, an HSC process, and a fluid catalytic cracking process.
- the operating conditions are not particularly limited, but the above heavy oil is used as a raw material and a coker pyrolysis apparatus is used, and preferably the reaction pressure is 0.8 MPa and the decomposition temperature is 400 to 600 ° C.
- the end point of the light oil used in the present invention is 380 ° C. or lower, preferably 350 ° C. or lower. A preferred lower limit is 310 ° C. When the end point exceeds 380 ° C., the fraction to be coke increases and the CTE of coke increases. The end point is measured based on the method described in JIS K 2254-4: 1998.
- the asphaltene component of the light oil used in the present invention is preferably less than 1% by mass, more preferably 0% by mass, and since the end point is 380 ° C. or less, it contains substantially no caulking component. . If a large amount of ingredients to be coked is included, the CTE and puffing of coke are adversely affected and cannot be sufficiently suppressed.
- the aroma component of the light oil used in the present invention is preferably 40% by volume or more, more preferably 50% by volume or more, from the viewpoint of compatibility with the heavy oil. A preferred upper limit is 70% by volume.
- the aroma component mentioned here is a coker gas oil measured in accordance with the Petroleum Institute Method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute.
- the volume percentage (volume%) of the total aromatic content based on the total amount.
- an aromatic component having two or more aromatic rings is preferably present in an amount of 20% by volume or more, more preferably 45% by volume or more. It is because it has excellent compatibility with heavy oil by having a polycyclic aromatic group containing two rings.
- two or more light oils may be used in combination.
- the light oil feedstock used in the present invention is not particularly limited as long as it can obtain a light oil whose end point obtained by the above process satisfies the above-described conditions, preferably The density at 15 ° C. is 0.8 g / cm 3 or more.
- Fluid catalytic cracking to obtain light oil is generally performed under the same conditions as fluid catalytic cracking to obtain heavy oil.
- the temperature in the delayed coking process for obtaining light oil is preferably 400 to 600 ° C., and the pressure is preferably 300 to 800 kPa. At such a temperature, the reaction can proceed mildly at a temperature at which coking proceeds (400 ° C. or higher). A higher pressure is preferable because it increases the coke yield, but varies depending on the process.
- the above-mentioned aroma components of heavy oil are those measured by the TLC-FID method.
- TLC-FID method a sample is divided into four components by a thin layer chromatography (TLC) into a saturated component, an aroma component, a resin component, and an asphaltene component, and then each component is detected with a flame ionization detector (FID). And the percentage of each component amount relative to the total component amount is used as the composition component value.
- a sample solution is prepared by dissolving 0.2 g ⁇ 0.01 g of a sample in 10 ml of toluene. Use a microsyringe to spot 1 ⁇ l at the lower end (0.5 cm position of the rod holder) of a silica gel rod-like thin layer (chroma rod) that has been baked in advance, and dry it with a dryer or the like.
- 10 microrods are taken as one set, and the sample is developed with a developing solvent.
- hexane is used for the first developing tank
- hexane / toluene (volume ratio 20:80)
- dichloromethane / methanol (volume ratio 95: 5) is used for the third developing tank.
- the saturated component is eluted and developed in the first developing tank using hexane as a solvent.
- an aroma component it elutes
- the developed chromato rod is set in a measuring instrument (for example, “Iatroscan MK-5” (trade name) manufactured by Diatron (currently Mitsubishi Chemical Yatron)), and the amount of each component is measured. The total amount of each component is obtained by summing the amounts of each component.
- a measuring instrument for example, “Iatroscan MK-5” (trade name) manufactured by Diatron (currently Mitsubishi Chemical Yatron)
- the light oil aroma component and asphaltene component were measured by the same method as the heavy oil aroma component.
- the method for producing petroleum coke according to the present invention will be described. At least the above light oil and heavy oil are mixed to produce a raw material oil, and the raw material oil is caulked. As a result, petroleum coke having a sufficiently small CTE and sufficiently suppressed puffing can be stably produced.
- the mixing ratio of heavy oil to light oil in the feed oil is preferably 5 to 30% by mass of the light oil in the feed oil. When the amount is less than 5% by mass, the effect of reducing the CTE and puffing of coke is not obtained so much. Moreover, when it exceeds 30 mass%, the coke yield of raw material oil may fall significantly, and the production amount of coke may fall. From the viewpoint of reducing the CTE of coke, the light oil in the feedstock is more preferably 10 to 30% by mass.
- a delayed coking method may be used. Specifically, under conditions where the coking pressure is controlled, raw coke is pyrolyzed and polycondensed with a delayed coker to produce raw coke, and the raw coke is calcined in a rotary kiln, shaft furnace, etc. to produce needle coke.
- the obtaining method is preferred.
- the pressure is 300 to 800 kPa and the temperature is 400 to 600 ° C.
- the calcination temperature is preferably 1000 to 1500 ° C.
- raw coke contains a large amount of moisture and volatile components
- calcined coke containing almost no of these components can be obtained by calcining at a high temperature of 1000 ° C. or higher.
- it exceeds 1500 degreeC implementation is not easy due to the temperature restrictions on an installation.
- the sulfur content of the petroleum coke thus obtained is preferably 0.3% by mass or less, and the thermal expansion coefficient is preferably 1.5 ⁇ 10 ⁇ 6 / ° C. or less, more preferably 1.3 ⁇ 10 ⁇ 6 / ° C. or lower.
- a preferable lower limit of the sulfur content is 0.1% by mass.
- a preferable lower limit of the thermal expansion coefficient is 1.0 ⁇ 10 ⁇ 6 / ° C.
- the thermal expansion coefficient of petroleum coke is preferably 1.5 ⁇ 10 ⁇ 6 / ° C. or less, more preferably 1.3 ⁇ 10 ⁇ 6 / ° C.
- puffing is preferably 0.2% or less.
- an appropriate amount of a binder pitch is added to the petroleum coke of the present invention and heated and mixed, and then extruded to produce a raw electrode.
- the method of carbonization and graphitization treatment is not particularly limited. Usually, firing is performed under an inert gas atmosphere such as nitrogen, argon, or helium, with a maximum temperature of 900 to 1500 ° C. and a maximum temperature holding time of 0 to 10 hours. Examples thereof include a method of graphitizing in a similar inert gas atmosphere and then having a maximum temperature of 2500 to 3200 ° C. and a maximum temperature holding time of 0 to 100 hours. After carbonization, it may be once cooled and subjected to the above heat treatment for graphitization again.
- Example 1 Desulfurized vacuum residue (sulfur content 500 mass ppm, density 0.88 g / cm 3 at 15 ° C.) is subjected to fluid catalytic cracking and fluid catalytic cracking residual oil (hereinafter referred to as “fluid catalytic cracking residual oil (A)”).
- the obtained fluid catalytic cracking residual oil (A) had an initial boiling point of 200 ° C., a sulfur content of 0.2% by mass, a nitrogen content of 0.1% by mass, and an aroma component of 65% by mass.
- fluid catalytic cracking light oil (A) desulfurized vacuum residue (sulfur content: 500 mass ppm, density: 0.88 g / cm 3 at 15 ° C.) is subjected to fluid catalytic cracking to produce light cycle oil (hereinafter referred to as “fluid catalytic cracking light oil (A)”).
- the obtained fluid catalytic cracking light oil (A) had an initial boiling point of 180 ° C., an end point of 350 ° C., an asphaltene component of 0% by mass, a saturated component of 47% by volume, and an aroma component of 53% by volume.
- hydrodesulfurized oil (A) hydrodesulfurized oil
- Desulfurized vacuum residue sulfur content 500 mass ppm, density 0.88 g / cm 3 at 15 ° C.
- hydrodesulfurized oil (A) sulfur content 0.3 mass%, nitrogen content 0.1 mass%, A feedstock obtained by mixing 2% by mass of asphaltene component, 70% by mass of saturation and 0.92 g / cm 3 of density at 15 ° C.
- fluid catalytic cracking residual oil (B) was obtained.
- the obtained fluid catalytic cracking residual oil (B) had an initial boiling point of 220 ° C., a sulfur content of 0.5 mass%, a nitrogen content of 0.1 mass%, and an aroma component of 79 mass%.
- the feedstock oil which mixed the fluid catalytic cracking residual oil (A), the fluid catalytic cracking residual oil (B), and the fluid catalytic cracking light oil (A) by mass ratio 5: 2: 3 was obtained. This raw material oil was put into a test tube and heat-treated at normal pressure and 500 ° C.
- calcined coke of a plurality of sizes pulverized to 1.4 mm or less stipulated in JIS Z-8801 are mixed at a predetermined ratio, and a binder pitch is added at a predetermined ratio and combined. Molded with an extruder. After baking at 1,000 ° C., a measurement piece was produced. The elongation in the length direction of the piece (from 200 ° C. to 300 ° C.) was measured, and the thermal expansion coefficient was measured. For puffing, calcined coke pulverized to 425 ⁇ m or less and a binder pitch were mixed at a predetermined ratio and molded into a cylinder. After baking at 1,000 ° C., a measurement piece was produced. The elongation in the length direction of the piece (from room temperature to 2,800 ° C.) was measured, and the linear expansion coefficient was measured.
- Example 2 Decomposed gas oil obtained by delayed coking process as raw material oil (sulfur content 0.2% by mass, density 0.92g / cm 3 at 15 ° C, saturation 36% by volume, aroma component 64% by volume, asphaltene component 0% by mass , Initial boiling point 220 ° C., final boiling point 340 ° C. (hereinafter referred to as “coker cracked diesel oil (A)”), fluid catalytic cracking residual oil (A), and fluid catalytic cracking residual oil (B) The same operation as in Example 1 was performed except that a mixture of 3: 5: 2 was used.
- Example 3 As feedstock oil, fluid catalytic cracking residual oil (A), fluid catalytic cracking residual oil (B), hydrodesulfurized oil (A), fluid catalytic cracking gas oil (A) are each in a mass ratio of 5: 2: 1.5: 1. The same procedure as in Example 1 was performed except that the mixture mixed in .5 was used.
- Example 4 As feedstock oil, fluid catalytic cracking residual oil (A), fluid catalytic cracking residual oil (B), hydrodesulfurized oil (A), and coker cracked light oil (A) are each in a mass ratio of 5: 2: 1.5: 1. The same procedure as in Example 1 was performed except that the mixture in 5 was used.
- Example 5 Desulfurized gas oil obtained by gas oil desulfurization equipment as raw material oil (density 0.90 g / cm 3 at 15 ° C., aroma component 25% by volume, asphaltene component 0% by mass, initial boiling point 180 ° C., final boiling point 350 ° C. (below) , "Desulfurized diesel oil (A)"), fluid catalytic cracking residual oil (A), and fluid catalytic cracking residual oil (B) mixed at a mass ratio of 3: 5: 2 The same procedure as in Example 1 was performed.
- Example 6 Other than using raw oil mixed with fluid catalytic cracking residual oil (A), fluid catalytic cracking residual oil (B), and coker cracked light oil (A) in a mass ratio of 7.5: 2: 0.5 was carried out in the same manner as in Example 1.
- Example 1 The raw oil used was a mixture of fluid catalytic cracking residual oil (A), fluid catalytic cracking residual oil (B), and hydrodesulfurized oil (A) in a mass ratio of 5.5: 2: 2.5. Except for this, the same procedure as in Example 1 was performed.
- Example 2 It carried out similarly to Example 1 except having used hydrodesulfurization oil (A) as raw material oil.
- Example 3 The same procedure as in Example 1 was performed except that fluid catalytic cracking residual oil (A) was used as the raw material oil.
- Example 4 The same procedure as in Example 1 was performed except that fluid catalytic cracking residual oil (B) was used as the raw material oil.
- Table 1 shows the sulfur and nitrogen contents of calcined coke obtained in Examples 1 to 6 and Comparative Examples 1 to 4. In addition, Table 1 shows the measurement results of the thermal expansion coefficient and puffing of the pieces obtained in Examples 1 to 6 and Comparative Examples 1 to 4.
- Table 2 shows the properties of fluid catalytic cracking residual oil (A) and fluid catalytic cracking residual oil (B), which are heavy oils. Hydrodesulfurized oil (A), fluid catalytic cracking light oil (A), coker cracked light oil
- Table 3 shows the properties of (A) and desulfurized light oil (A).
- the sulfur content of the calcined coke obtained in Examples 1 to 6 was 0.3% by mass or less.
- the pieces obtained in Examples 1 to 6 had a thermal expansion coefficient of 1.5 ⁇ 10 ⁇ 6 / ° C. or less and a puffing of 0.2% or less. Therefore, it was shown that the method for producing petroleum coke according to the present invention can sufficiently reduce the thermal expansion coefficient and sufficiently suppress puffing.
Abstract
Description
また、本発明においては、上記石油コークスの製造方法によって得られる石油コークスを提供する。
本発明で用いられる重質油のアロマ成分は、50質量%以上であり、好ましくは70質量%以上である。好ましい上限値は、90質量%である。このような範囲であれば、良好なバルクメソフェーズを形成し、コーキング反応の進行を促進させるからである。
本発明で用いられる重質油の硫黄分は、0.5質量%以下であり、好ましくは0.4質量%以下であり、より好ましくは0.3質量%以下である。好ましい下限値は、0.1質量%である。硫黄分が0.5質量%を超えると、石油コークスのパッフィングを十分に抑えることができないからである。硫黄分は、JIS M 8813-附属2:2006に記載された方法に基づき測定される。
本発明で用いられる重質油の窒素分は、0.2質量%以下であり、好ましくは0.15質量%以下であり、より好ましくは0.10質量%以下である。好ましい下限値は、0.01質量%である。窒素分が0.2質量%を超えると、石油コークスのパッフィングを十分に抑えることができないからである。窒素分は、JIS M 8813-附属4:2006に記載された方法に基づき測定される。
また、本発明において、重質油は2種以上を併用してもよい。
減圧蒸留残油(VR)は、原油を常圧蒸留装置にかけて、ガス・軽質油・常圧残渣油を得た後、この常圧残渣油を、例えば、10~30Torrの減圧下、加熱炉出口温度320~360℃の範囲で変化させて得られる減圧蒸留装置のボトム油である。
流動接触分解に用いられる触媒としては、例えばゼオライト触媒、シリカアルミナ触媒、又はこれらの触媒に白金等の貴金属を担持したもの等が挙げられる。
また、かかる軽質油を得るために用いるプロセスは特に限定されるものではない。例えば、ディレードコーキングプロセス、ビスブレーキングプロセス、ユリカプロセス、HSCプロセス、流動接触分解プロセス等が挙げられる。
運転条件は特に限定されるものではないが、上記の重質油を原料としてコーカー熱分解装置を用い、好ましくは反応圧力を0.8MPa、分解温度を400~600℃で処理する。
本発明で用いられる軽質油の終留点は、380℃以下であり、好ましくは350℃以下である。好ましい下限値は、310℃である。終留点が380℃を超えると、コークス化する留分が増加し、コークスのCTEは高くなる。終留点は、JIS K 2254-4:1998に記載された方法に基づき測定される。
本発明で用いられる軽質油のアスファルテン成分は、好ましくは1質量%未満であり、より好ましくは0質量%であり、また終留点が380℃以下であるため実質上コーキングする成分をほとんど含まない。コーキングする成分を多く含むと、コークスのCTE及びパッフィングに悪影響を与え、それらを十分に抑えることができない。
本発明で用いられる軽質油のアロマ成分は、重質油との相溶性の観点から、好ましくは40容量%以上であり、より好ましくは50容量%以上である。好ましい上限値は、70容量%である。なお、ここでいうアロマ成分とは、社団法人石油学会により発行されている石油学会法JPI-5S-49-97「炭化水素タイプ試験方法-高速液体クロマトグラフ法」に準拠され測定されるコーカー軽油全量基準の全芳香族含有量の容量百分率(容量%)をいう。
本発明で用いられる軽質油においては、2環以上の芳香族を有するアロマ成分が、好ましくは20容量%以上、さらに好ましくは45容量%以上存在する。2環を含む多環芳香族を有することによって、重質油との相溶性に優れるからである。
また、本発明において、軽質油は2種以上を併用してもよい。
軽質油を得るための流動接触分解は、一般的に上記した重質油を得るための流動接触分解と同一の条件下で行われる。
また、軽質油を得るためのディレードコーキングプロセスにおける温度は、好ましくは400~600℃であり、圧力は、好ましくは300~800kPaである。このような温度であれば、コーキングが進行する温度(400℃以上)で、かつマイルドに反応を進行させることができる。圧力は高い方がコークス収率増加となるため好ましいが、プロセスにより異なる。
少なくとも上記した軽質油と重質油を混合して原料油を作製し、原料油をコーキングする。これにより、CTEが十分に小さく、かつ、パッフィングが十分に抑制された石油コークスを安定的に製造することができる。
原料油中における重質油と軽質油の混合比は、原料油中の軽質油が好ましくは5~30質量%となるように配合する。5質量%未満である場合には、コークスのCTE、Puffingを低下させる効果があまり得られない。また、30質量%を超える場合には、原料油のコークス収率が大きく低下し、コークスの生産量が低下する場合がある。コークスのCTEを低下させる観点から、より好ましくは、原料油中の軽質油は10~30質量%である。
また、か焼温度は、好ましくは1000~1500℃である。生コークスは、多量の水分と揮発分を含んでいるため、1000℃以上の高温でか焼することによってこれらの成分をほとんど含まないか焼コークスが得られる。また、1500℃を超えると、設備上の温度制約により実施が容易でない。
また、得られた石油コークスの硫黄分、窒素分の含有量が低いため、パッフィングが0.2%以下の石油コークスが得られる。この石油コークスを用いて良好な黒鉛電極製品を製造するためには、石油コークスの熱膨張係数は好ましくは1.5×10-6/℃以下、より好ましくは1.3×10-6/℃以下であり、かつ、パッフィングは好ましくは0.2%以下である。
炭化および黒鉛化処理の方法は、特に限定されないが、通常は、窒素、アルゴン又はヘリウム等の不活性ガス雰囲気下で最高到達温度900~1500℃、最高到達温度の保持時間0~10時間で焼成(炭化)され、次いで同様な不活性ガス雰囲気下、最高到達温度2500~3200℃、最高到達温度保持時間0~100時間の黒鉛化処理する方法を挙げることができる。炭化の後、一旦冷却して再度黒鉛化のために上記熱処理を施してもよい。
(実施例1)
脱硫減圧残油(硫黄分500質量ppm、15℃における密度0.88g/cm3)を流動接触分解し、流動接触分解残油(以下、「流動接触分解残油(A)」と記す。)を得た。得られた流動接触分解残油(A)の初留点は200℃、硫黄分は0.2質量%、窒素分は0.1質量%、アロマ成分は65質量%であった。
次に、脱硫減圧残油(硫黄分500質量ppm、15℃における密度0.88g/cm3)を流動接触分解し、ライトサイクル油(以下、「流動接触分解軽油(A)」と記す。)を得た。得られた流動接触分解軽油(A)の初留点は180℃、終留点は350℃、アスファルテン成分は0質量%、飽和分は47容量%、アロマ成分は53容量%であった。
また、硫黄分が3.5質量%の常圧蒸留残油を、Ni-Mo触媒の存在下、水素化分解率が30%以下となるように水素化脱硫し、水素化脱硫油(以下、「水素化脱硫油(A)」と記す。)を得た。脱硫減圧残油(硫黄分500質量ppm、15℃における密度0.88g/cm3)と、水素化脱硫油(A)(硫黄分が0.3質量%、窒素分が0.1質量%、アスファルテン成分が2質量%、飽和分が70質量%、15℃における密度が0.92g/cm3)とを質量比1:2で混合した原料油を流動接触分解し、流動接触分解残油(以下、「流動接触分解残油(B)」と記す。)を得た。得られた流動接触分解残油(B)の初留点は220℃、硫黄分は0.5質量%、窒素分は0.1質量%、アロマ成分は79質量%であった。
次に、流動接触分解残油(A)、流動接触分解残油(B)、流動接触分解軽油(A)それぞれを質量比5:2:3で混合した原料油を得た。この原料油を試験管に入れ、常圧、500℃で3時間熱処理を行い、コークス化した。次に、生成したコークスを1000℃で5時間焼成してか焼コークスを得た。
また、か焼コークスに石炭系のバインダーピッチを30質量%加え、押し出し成形器で円柱状のピースを作製した。このピースを、マッフル加熱炉を用いて1000℃で1時間焼成し、焼成後の熱膨張係数を測定した。更に、ピースを室温から2800℃まで熱処理し、この過程での膨張の度合いをパッフィング(Puffing)として測定した。
熱膨張係数については、JIS Z-8801にて規定される1.4mm以下に粉砕された複数種のサイズのか焼コークスを所定の割合で混合し、バインダーピッチを所定の割合で加えて捏合し、押し出し成型器にて成型した。1,000℃にて焼成後、測定用ピースを作製した。ピースの長さ方向への伸び(200℃から300℃まで)を測定し、熱膨張係数を測定した。
パッフィングについては、425μm以下に粉砕したか焼コークスとバインダーピッチを所定の割合で混合し、円柱に成型した。1,000℃で焼成後、測定用ピースを作製した。ピースの長さ方向への伸び(室温から2,800℃まで)を測定し、線膨張率を測定した。
原料油として、ディレードコーキングプロセスで得られた分解軽油(硫黄分0.2質量%、15℃における密度0.92g/cm3、飽和分36容量%、アロマ成分64容量%、アスファルテン成分0質量%、初留点220℃、終留点340℃(以下、「コーカー分解軽油(A)」と記す。))、流動接触分解残油(A)、及び流動接触分解残油(B)を質量比3:5:2で混合したものを用いたこと以外は、実施例1と同様に行った。
原料油として、流動接触分解残油(A)、流動接触分解残油(B)、水素化脱硫油(A)、流動接触分解軽油(A)それぞれを質量比5:2:1.5:1.5で混合したものを用いたこと以外は、実施例1と同様に行った。
原料油として、流動接触分解残油(A)、流動接触分解残油(B)、水素化脱硫油(A)、コーカー分解軽油(A)それぞれを質量比5:2:1.5:1.5で混合したものを用いたこと以外は、実施例1と同様に行った。
原料油として、軽油脱硫装置により得られた脱硫軽油(15℃における密度0.90g/cm3、アロマ成分25容量%、アスファルテン成分0質量%、初留点180℃、終留点350℃(以下、「脱硫軽油(A)」と記す。))、流動接触分解残油(A)、及び流動接触分解残油(B)を質量比3:5:2で混合したものを用いたこと以外は、実施例1と同様に行った。
原料油として、流動接触分解残油(A)、流動接触分解残油(B)、及びコーカー分解軽油(A)を質量比7.5:2:0.5で混合したものを用いたこと以外は、実施例1と同様に行った。
原料油として、流動接触分解残油(A)、流動接触分解残油(B)、水素化脱硫油(A)それぞれを質量比5.5:2:2.5で混合したものを用いたこと以外は、実施例1と同様に行った。
原料油として、水素化脱硫油(A)を用いたこと以外は、実施例1と同様に行った。
原料油として、流動接触分解残油(A)を用いたこと以外は、実施例1と同様に行った。
原料油として、流動接触分解残油(B)を用いたこと以外は、実施例1と同様に行った。
Claims (5)
- 終留点が380℃以下である軽質油と、初留点が200℃以上であり、アロマ成分が50質量%以上であり、硫黄分が0.5質量%以下で窒素分が0.2質量%以下である重質油とを少なくとも含む原料油をコーキングする工程を含む石油コークスの製造方法。
- 前記原料油中の前記軽質油が、10~30質量%である請求項1に記載の石油コークスの製造方法。
- 前記軽質油が、流動接触分解又はディレードコーキング由来であり、前記重質油が、流動接触分解により得られる請求項1又は2に記載の石油コークスの製造方法。
- 請求項1~3のいずれか1項に記載の石油コークスの製造方法によって得られる石油コークス。
- 硫黄分が0.3質量%以下であり、熱膨張係数が1.5×10-6/℃以下である請求項4に記載の石油コークス。
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