JP4375646B2 - Kerosene manufacturing method - Google Patents

Description

【００６１】
表１に示すように、ＣＡＴが４００℃である場合には水素化分解灯油１００％であっても（実施例８）、密度、引火点等の性状に問題はなく、また酸化開始温度、全不溶分共に品質上問題はない結果が得られた。またＣＡＴが４００℃以上の場合であっても、水素化精製灯油と混合することにより同様の結果を得ることができた（実施例１〜７）。一方、ＣＡＴを４０６℃とした１００％水素化分解灯油の基材は、十分高い酸化開始温度を示したが、全不溶分が多過ぎ品質が十分とはいえなかった。また、ＣＡＴを４１３℃，４１６℃とした１００％水素化分解灯油の基材は、酸化開始温度、全不溶分共に十分な品質は得られなかった。
【００６２】
表２および表３に水素化残油脱硫灯油を水素化精製灯油に混合した場合の結果を示す。
【００６３】
【表２】

【００６４】
【表３】

【００６５】
上記表２，３に示すように、水素化残油脱硫灯油１００容量％からなる各基材は蒸留終点にかかわらず、酸化開始温度、全不溶分共に問題があり、製品灯油としての使用に堪え得るものではなかった。これに対して、実施例９〜２１の混合灯油は、いずれも十分な品質を有するものであった。特に、残油脱硫灯油の蒸留終点が２２０℃以下の場合４％混合しても酸化開始温度、全不溶分共に品質上問題はなかった（実施例９〜１１）。また、蒸留終点が２４０℃，２６０℃の場合も、２％混合した場合の製品灯油は燃焼性、安定性ともに必要な品質を満たした（実施例１５，１６）。これに対し、水素化残油脱硫灯油を５容量％混合したものは、蒸留終点が１８０℃であっても不溶分が０．３０より大きく問題があった（比較例１）。
【００６６】
表４および表５に未洗灯油に残油脱硫灯油を混合後、水素化脱硫した場合の結果を示す。
【００６７】
【表４】

【００６８】
【表５】

【００６９】
上記表４，５に示すように、実施例２２〜３４の混合灯油は、いずれも十分な品質を有するものであった。特に、残油脱硫灯油の蒸留終点が２２０℃以下の場合４％混合しても酸化開始温度、全不溶分共に品質上問題はなかった（実施例２２〜２４）。また、蒸留終点が２４０℃，２６０℃の場合も、２％混合した場合の製品灯油は燃焼性、安定性ともに必要な品質を満たした（実施例２８，２９）。これに対し、残油脱硫灯油を５容量％混合したものは、蒸留終点が１８０℃であっても不溶分が０．３０より大きく問題があった（比較例２）。
【００７０】
表６に、残油脱硫ナフサワイドカットを原油に混合後、原油蒸留装置で蒸留し灯油留分を回収した場合の結果を示す。
【００７１】
【表６】

【００７２】
上記表６に示すように、実施例３５〜４７の灯油は、いずれも酸化開始温度、全不溶分共に品質上問題はなく、１００％の原油由来灯油と比較しても遜色ないものであった。
【００７３】
【発明の効果】
以上説明したように、本発明によれば、従来は製品灯油として使用されなかった残油脱硫灯油や、水素化分解灯油を用いて現行の製品灯油と遜色のない高品質の製品灯油を製造することが可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing kerosene, and more particularly to a method for producing high-quality kerosene using residual oil desulfurized kerosene or hydrorefined kerosene as a raw material.
[0002]
[Prior art]
At present, kerosene is used for lighting, heating, kitchens, etc., and more than 85% is used in ordinary households, and kerosene suitable for core up-and-down type oil stoves that have been used for a long time has been distributed. Yes. Therefore, it is desirable that the kerosene has a certain range of sulfur content from the viewpoint of the indoor environment, smoke point and oxidation start temperature from the viewpoint of combustibility, and flash point and storage stability from the viewpoint of safety. In order to satisfy these conditions, conventionally, only hydrorefined kerosene obtained by hydrorefining a fraction having a boiling range of 145 to 280 ° C. obtained by distilling crude oil is used. The cracked kerosene obtained by cracking a high fraction has hardly been used.
[0003]
On the other hand, recently, due to changes in the domestic demand structure, it has become a challenge to make heavy oil fractions into light petroleum products, and various crackers have been introduced. At present, products obtained from these crackers are used for gasoline, light oil, A heavy oil, and the like. However, the distillation range obtained from these devices is a fraction (cracked kerosene) in the range of 145 to 280 ° C., particularly the residual oil desulfurized kerosene obtained from the residual oil desulfurizer and the hydrocracked kerosene obtained from the hydrocracker. Has not been used as kerosene.
[0004]
Generally, residual desulfurized kerosene is further refined by FCC (catalytic cracking equipment) to produce a base material of gasoline or heavy oil. In this case, there is a problem in that purification by FCC is costly, and therefore, the environmental load from the viewpoint of LCA is increased. In addition, it is only to some extent that residual desulfurized kerosene is used as part of heavy oil outside Japan.
[0005]
On the other hand, hydrocracked kerosene has been mainly used for jet fuel. Recently, however, it has been reported that jet fuel mainly composed of hydrocracked kerosene has poor lubricity, and there is a problem that it is becoming difficult to use much hydrocracked kerosene as jet fuel.
[0006]
When the fraction obtained by this hydrocracking is compared with the fraction obtained by other catalytic cracking, the hydrocracked kerosene has less olefin and the desulfurization of the compound containing sulfur proceeds. One of the features is that there are few. On the other hand, however, decomposition of cyclic paraffins and polycyclic aromatics called naphthenes is not so easy, and as a result of hydrocracked oils, naphthenes and naphthenobenzenes are more common than straight-run kerosene. It has been known. It is known that burning of kerosene containing a large amount of naphthene and naphthenobenzene, especially naphthenobenzene, adversely affects the combustibility. In addition, slight changes in the CAT (catalyst average temperature) of the hydrocracking apparatus greatly change the yield and composition of each fraction obtained, and the properties of hydrocracked kerosene can also be obtained from other processes. It was not stable compared to the fraction. For this reason, it has been considered difficult to produce kerosene with stable quality from the kerosene fraction obtained from the hydrocracking process.
[0007]
Residue desulfurized kerosene has not been used because it has a high olefin content and lacks stability, and has a high aromatic content and its smoke point does not meet the JIS standard for kerosene.
[0008]
[Problems to be solved by the invention]
In view of the change in the demand structure, the object of the present invention is to Stable quality from kerosene fraction obtained from hydrocracking process It is to provide a method for producing a product kerosene.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a new method for producing kerosene for combustion equipment such as a petroleum fan heater by using residual desulfurized kerosene or hydrocracked kerosene as product kerosene.
[0010]
That is, the first method for producing kerosene according to the present invention comprises hydrocracking at least one selected from vacuum distilled light oil, catalytic cracking light oil, pyrolysis light oil and debris oil at a CAT (catalyst average temperature) of 400 ° C. or lower. And a step of recovering the kerosene fraction.
[0011]
The second method for producing kerosene according to the present invention comprises a step of hydrocracking at least one selected from vacuum distilled light oil, catalytic cracking light oil, pyrolysis light oil and degassed oil, and hydrogenation in which the kerosene fraction is recovered. It comprises a step of obtaining cracked kerosene and a step of mixing the hydrocracked kerosene with hydrorefined kerosene.
[0012]
In the third method for producing kerosene according to the present invention, hydrogenated residual kerosene obtained by hydrodesulfurizing residual desulfurized kerosene to hydrorefined kerosene is 0.1% by volume based on the total amount after mixing. It has the process of mixing 4 volume% or less above.
[0013]
The fourth method for producing kerosene according to the present invention comprises mixing unwashed kerosene with residual desulfurized kerosene from 0.1 vol% to 4 vol% based on the total amount after mixing, and mixing the kerosene with hydrogen Characterized by having a step of hydrodesulfurization.
[0014]
The fifth method for producing kerosene according to the present invention comprises a step of collecting a residual oil desulfurized naphtha wide cut from a residual oil desulfurized naphtha to 200 to 280 ° C. into crude oil, and then distilling the crude oil with a crude oil distillation apparatus to collect a kerosene fraction It is characterized by having.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the production method of the present invention will be described in detail.
First, a method for producing kerosene comprising recovering a kerosene fraction obtained by hydrocracking at least one selected from vacuum-distilled gas oil, catalytic cracking gas oil, pyrolysis gas oil, and degassed oil at CAT 400 ° C. or lower (first step) Manufacturing method) will be described. Hydrocracking here refers to the introduction of vacuum distillation diesel oil, catalytic cracking diesel oil, pyrolysis diesel oil, etc. into a single-stage or two-stage reactor packed with a catalyst having both amorphous and zeolite resolution and hydrogenation ability. And a reaction pressure of 70 to 200 kg / cm in the presence of excess hydrogen. ² , Refers to a process for producing LPG, naphtha, kerosene, light oil, lubricating base oil, etc. at a reaction temperature (= CAT) of 340 to 450 ° C.
[0016]
By setting the CAT in hydrocracking to 400 ° C. or less, kerosene suitable for combustion equipment can be produced. The hydrocracked kerosene thus produced preferably satisfies the following properties from the viewpoint of the properties of the kerosene produced. That is, it is desirable that the sulfur content is 80 ppm or less, desirably 65 ppm or less, more desirably 60 ppm or less, and most desirably 40 ppm or less from the viewpoint of the indoor environment when used in a normal kerosene combustion device. From the viewpoint of combustibility, the end point of distillation is preferably 281 ° C. or lower, more preferably 280 ° C. or lower, and most preferably 279 ° C. or lower. From the viewpoint of safety, the flash point is preferably 40 ° C. or higher, more preferably 42 ° C. or higher, and still more preferably 44 ° C. or higher. Similarly, from the viewpoint of safety, the initial distillation temperature is preferably 145 ° C. or higher, more preferably 147 ° C. or higher, and most preferably 149 ° C. or higher.
[0017]
Next, each kerosene base material to be mixed in the novel method for producing kerosene (the second to fourth production methods) having a step of mixing various kerosene base materials under specific conditions will be described in detail.
[0018]
The hydrorefined kerosene used in the present invention means kerosene obtained by hydrorefining straight run kerosene (unwashed kerosene) obtained by distilling crude oil. As a method of hydrorefining, straight kerosene is passed through a one-stage or two-stage reaction cylinder filled with an alumina catalyst supporting molybdenum on an alumina support, and a pressure of 10 to 40 kg / cm. ² The method of causing the desulfurization reaction at a temperature of 250 to 350 ° C. is mainly used.
[0019]
This hydrorefined kerosene preferably satisfies the following properties from the viewpoint of the properties of kerosene produced by the production method of the present invention. That is, it is desirable that the sulfur content is 80 ppm or less, desirably 65 ppm or less, more desirably 60 ppm or less, and most desirably 40 ppm or less from the viewpoint of the indoor environment when used in a normal kerosene combustion device. From the viewpoint of combustibility, the smoke point is preferably 21 mm or less, more preferably 23 mm or less. Further, from the viewpoint of combustibility, the oxidation start temperature is 207 ° C. or higher, more desirably 208 ° C. or higher, and most preferably 209 ° C. or higher. From the viewpoint of combustibility, the 95% distillation temperature is preferably 270 ° C. or less, more preferably 269 ° C. or less, and most preferably 268 ° C. or less. From the viewpoint of combustibility, the end point of distillation is preferably 281 ° C. or lower, more preferably 280 ° C. or lower, and most preferably 279 ° C. or lower. From the viewpoint of safety, the flash point is preferably 40 ° C. or higher, more preferably 42 ° C. or higher, and still more preferably 44 ° C. or higher. Similarly, from the viewpoint of safety, the initial distillation temperature is preferably 145 ° C. or higher, more preferably 147 ° C. or higher, and most preferably 149 ° C. or higher. Also, from the viewpoint of stability, the total insoluble content in the storage stability test is desirably 0.3 mg / 100 ml or less, more preferably 0.2 mg / 100 ml or less, and 0.1 mg / 100 ml or less. Is most preferred.
[0020]
Moreover, the hydrocracking kerosene used for this invention means the kerosene obtained by hydrocracking decompression light oil etc. as above-mentioned. In particular, the hydrocracked kerosene used as the kerosene base material of the present invention usually has a CAT of 416 ° C. or lower as a hydrocracking method. When CAT is higher than 416 ° C., stability and combustibility are lowered, and abnormal combustion may occur when used in a core type stove or a fan heater.
[0021]
This hydrocracked kerosene preferably satisfies the following properties from the viewpoint of the properties of kerosene produced by the production method of the present invention. That is, it is desirable that the sulfur content is 80 ppm or less, desirably 65 ppm or less, more desirably 60 ppm or less, and most desirably 40 ppm or less from the viewpoint of the indoor environment when used in a normal kerosene combustion device. From the viewpoint of combustibility, the end point of distillation is preferably 281 ° C. or lower, more preferably 280 ° C. or lower, and most preferably 279 ° C. or lower. From the viewpoint of safety, the flash point is preferably 40 ° C. or higher, more preferably 42 ° C. or higher, and still more preferably 44 ° C. or higher. Similarly, from the viewpoint of safety, the initial distillation temperature is preferably 145 ° C. or higher, more preferably 147 ° C. or higher, and most preferably 149 ° C. or higher.
[0022]
The residual oil desulfurized kerosene used in the present invention means kerosene obtained by desulfurizing the residual oil. As a desulfurization method, after removing solid impurities with a filter, it is mixed with hydrogen gas and a pressure of 140 to 250 kg / cm. ² Those that cause a desulfurization reaction at a temperature of 350 to 430 ° C. are used.
[0023]
In general, the residual desulfurized kerosene has a distillation end point of 280 ° C. or lower from the viewpoint of stability. When the distillation end point exceeds 280 ° C., the stability is extremely lowered, and when used in product kerosene, there is a risk of causing deterioration due to storage.
[0024]
Furthermore, the hydrogenated residual oil desulfurized kerosene used in the present invention means kerosene obtained by subjecting the above-mentioned residual oil desulfurized kerosene to hydrogenation treatment (hydrodesulfurization). As a hydrotreating method, straight-run kerosene is passed through a one-stage or two-stage reaction cylinder filled with an alumina catalyst supporting molybdenum on an alumina support, and a pressure of 10 to 40 kg / cm. ² The method of causing the desulfurization reaction at a temperature of 250 to 350 ° C. is mainly used.
[0025]
This hydrogenated residual oil desulfurized kerosene preferably satisfies the following properties from the viewpoint of the properties of kerosene produced by the production method of the present invention. That is, it is desirable that the sulfur content is 80 ppm or less, desirably 65 ppm or less, more desirably 60 ppm or less, and most desirably 40 ppm or less from the viewpoint of the indoor environment when used in a normal kerosene combustion device. From the viewpoint of combustibility, the smoke point is preferably 21 mm or less, more preferably 23 mm or less. From the viewpoint of combustibility, the end point of distillation is preferably 260 ° C. or lower, more preferably 240 ° C. or lower, and most preferably 220 ° C. or lower. From the viewpoint of safety, the flash point is preferably 40 ° C. or higher, more preferably 42 ° C. or higher, and still more preferably 44 ° C. or higher. Similarly, from the viewpoint of safety, the initial distillation temperature is preferably 145 ° C. or higher, more preferably 147 ° C. or higher, and most preferably 149 ° C. or higher.
[0026]
Next, a method for producing kerosene comprising mixing these kerosene base materials will be described.
[0027]
First, the case where the hydrocracked kerosene is mixed with the hydrorefined kerosene (second production method) will be described. The upper limit of the ratio of kerosene after mixing of hydrocracked kerosene is 50% by volume when CAT is 413 ° C or higher and 416 ° C or lower.
-When CAT is 406 ° C or higher and 413 ° C or lower, the upper limit is the amount calculated by Equation 1 below.
Mixing amount (volume%) = − 2.857 × CAT (° C.) + 1230 (Formula 1)
・ CAT 400 ° C to 406 ° C In the following cases, the upper limit is the amount calculated by Equation 2 below.
Mixing amount (volume%) = − 5 × CAT (° C.) + 2100 (Formula 2)
-When CAT is 400 ° C or lower, there is no restriction on the mixing amount.
[0028]
Next, the case where the hydrogenated residual oil desulfurized kerosene is mixed with the hydrofinished kerosene (third production method) will be described. The ratio of the total amount of kerosene after mixing with the hydrogenated residual oil desulfurized kerosene is 0.1% by volume or more and 4% by volume or less. Hydrogenated residual oil desulfurized kerosene has a relatively high aromatic content and can be mixed within the range that does not lower the smoke point, so that the calorific value can be improved and the fuel consumption rate per capacity can be reduced. It is desirable to mix 1% by volume or more. When the mixing ratio exceeds 4% by volume, the stability is deteriorated, and it deteriorates during storage, which may cause abnormal combustion when used in a stove. When the distillation end point of hydrogenated residual oil desulfurized kerosene exceeds 260 ° C., the mixing ratio is preferably 2% by volume or less from the viewpoint of stability.
[0029]
Next, the case where hydrodesulfurization is performed after mixing residual oil desulfurized kerosene with unwashed kerosene (fourth production method) will be described. In this case as well (the third production method), the ratio of the total amount of kerosene after mixing the residual desulfurized kerosene is 0.1% by volume or more and 4% by volume or less. Hydrogenated residual oil desulfurized kerosene has a relatively high aromatic content and can be mixed within the range that does not lower the smoke point, so that the calorific value can be improved and the fuel consumption rate per capacity can be reduced. It is desirable to mix 1% by volume or more. When the mixing ratio exceeds 4% by volume, the stability is lowered and there is a risk of causing deterioration during storage. When the distillation end point of hydrogenated residual oil desulfurized kerosene exceeds 260 ° C., the mixing ratio is preferably 2% by volume or less from the viewpoint of stability.
[0030]
It can also be increased by mixing residual oil desulfurized naphtha with a wide cut of residual oil desulfurized naphtha from 200 to 280 ° C into crude oil, distilling it with a topper (crude oil distillation unit), taking out the kerosene fraction, and hydrodesulfurizing it. Quality kerosene can be manufactured (fifth manufacturing method). Also in this case, the ratio of the kerosene content of the residual oil desulfurized naphtha wide cut to the total amount of kerosene in the crude oil after mixing is 0.1% by volume or more and 4 volumes, as in the production method of (third production method). It is preferable that the residual oil desulfurized naphtha wide cut and the kerosene content present in the crude oil are respectively calculated and mixed so that the ratio is less than or equal to%. Residual oil desulfurized naphtha wide cut has a relatively high aromatic content, and if it is in a range that does not lower the smoke point, it can be mixed to improve the heat value and reduce the fuel consumption rate per capacity. It is desirable to mix 1% or more. When the mixing ratio exceeds 4% by volume, the stability is lowered and there is a risk of causing deterioration during storage. When the distillation end point of the residual oil desulfurized naphtha wide cut exceeds 260 ° C., the mixing ratio is preferably 2% by volume or less from the viewpoint of stability.
[0031]
It is also conceivable to mix two or more selected from hydrocracked kerosene, residual oil desulfurized kerosene, and hydrogenated residual oil desulfurized kerosene with hydrorefined kerosene. Also in this case, as in the case of the above (third production method) or (fourth production method), the calculated residual oil desulfurized kerosene ratio in the mixed kerosene is 0.1% by volume or more. It is necessary to be 4% by volume or less.
[0032]
Kerosene produced by the production method of the present invention has a 95% by volume distillation temperature (T ₉₅ There are no particular restrictions on the distillation properties other than), but it is desirable that the following properties are satisfied. The distillation properties referred to herein all mean values measured by the atmospheric distillation test method defined in JIS K 2254 “Petroleum products—distillation test method”.
Initial boiling point (IBP): 145-165 ° C
10 vol% distillation temperature (T _Ten ): 155-200 ° C
30% by volume distillation temperature (T ₃₀ ): 170-225 ° C
50 vol% distillation temperature (T ₅₀ ): 180-245 ° C
70 vol% distillation temperature (T ₇₀ ): 190-265 ° C
90 vol% distillation temperature (T ₉₀ ): 205-270 ° C
Distillation end point (EP): 220-281 ° C
[0033]
The initial boiling point is preferably 140 ° C. or higher, more preferably 142 ° C. or higher, and even more preferably 145 ° C. or higher, from the viewpoint of preventing adverse effects on safety due to a reduction in flash point. On the other hand, it is preferably 165 ° C. or lower, more preferably 162 ° C. or lower, and further preferably 160 ° C. or lower from the viewpoint of ignition characteristics at low temperatures.
[0034]
T _Ten Is preferably 155 ° C. or more, more preferably 160 ° C. or more, and preferably 162 ° C. or more from the viewpoint of preventing an unfavorable impact on safety due to a decrease in flash point and reducing odor during refueling. Even more preferred. On the other hand, it is preferably 200 ° C. or less, more preferably 195 ° C. or less, and further preferably 190 ° C. or less from the viewpoint of ignition characteristics at low temperatures.
[0035]
T ₃₀ Is preferably 170 ° C. or higher, more preferably 172 ° C. or higher, and even more preferably 175 ° C. or higher, from the viewpoints of odor reduction and calorific value during refueling. On the other hand, it is preferably 225 ° C. or less, more preferably 220 ° C. or less, and further preferably 216 ° C. or less from the viewpoint of ignition characteristics at low temperatures.
[0036]
T ₅₀ Is preferably 180 ° C. or higher, more preferably 183 ° C. or higher, and still more preferably 185 ° C. or higher from the viewpoint of the amount of heat generated. On the other hand, from the viewpoint of combustibility, it is preferably 245 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 238 ° C. or lower.
[0037]
T ₇₀ Is preferably 190 ° C. or higher, more preferably 193 ° C. or higher, and still more preferably 195 ° C. or higher. On the other hand, from the viewpoint of combustibility, it is preferably 265 ° C. or lower, more preferably 261 ° C. or lower, and further preferably 257 ° C. or lower.
[0038]
T ₉₀ Is preferably 205 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 215 ° C. or higher from the viewpoint of calorific value. On the other hand, from the viewpoint of combustibility, it is preferably 270 ° C. or lower, more preferably 269 ° C. or lower, and further preferably 268 ° C. or lower.
[0039]
The end point of distillation is preferably 281 ° C. or lower from the viewpoint of stability and flammability, more preferably 280 ° C. or lower, and even more preferably 279 ° C. or lower. On the other hand, when the distillation end point is less than 220 ° C., the fuel consumption rate is deteriorated when burned with an oil fan heater. Therefore, the temperature is preferably 220 ° C. or more, and more preferably 225 ° C. or more.
[0040]
Further, in the kerosene produced by the production method of the present invention, there is no particular limitation on the content of the saturates, olefins, and aromatics, but it is desirable to satisfy the following (note that the saturates here, Aromatic content and olefin content mean volume% of saturated content, olefin content, and aromatic content measured in accordance with the Fluorescent Indicator Adsorption Method (FIA) of “Petroleum Products-Ingredient Testing Method” stipulated in JIS K2536. To do).
Saturated content (S) 68-99.9% by volume
Olefin content (O) 0-0.5% by volume
Aromatic content (A) 0.1-30% by volume
[0041]
The saturated content is preferably 68% by volume or more, more preferably 72% by volume or more, and still more preferably 75% by volume or more from the viewpoint of combustibility. Further, the saturated content is preferably 99.9% by volume or less, more preferably 97% by volume or less, and still more preferably 90% by volume or less from the viewpoint of heat generation.
[0042]
In the kerosene produced by the production method of the invention, the aromatic content is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, and further preferably 1% by volume from the viewpoint of the calorific value. Further, from the viewpoint of combustibility, it is preferably 30% by volume or less, more preferably 25% by volume or less, and further preferably 20% by volume or less.
[0043]
In the kerosene produced by the production method of the present invention, the olefin content is preferably 0.5% by volume or less, more preferably 0.3% by volume or less, from the viewpoint of storage stability of kerosene. It is even more desirable to be less than 1% by volume.
[0044]
In the kerosene produced by the production method of the invention, there is no particular limitation on the smoke point, but it is preferably 21 mm or more, more preferably 22 mm or more from the viewpoint of combustibility, and 23 mm or more. Is even more preferred. The smoke point here means a value measured by the method defined in JIS K 2537 “Petroleum products—aviation turbine fuel and kerosene—smoke point test method”.
[0045]
In the kerosene produced by the production method of the invention, there is no particular limitation on the corrosion of the copper plate, but 1a or 1b is desirable and 1a is more desirable from the viewpoint of corrosiveness to the oil fan heater. In addition, copper plate corrosion here means the value measured by the copper plate corrosion test method prescribed | regulated by JISK2513 "Petroleum product-copper plate corrosion test method".
[0046]
In the kerosene produced by the production method of the invention, the density at 15 ° C. is not particularly limited, but from the point of fuel consumption rate, 750 kg / m ^Three Or more, preferably 770 kg / m ^Three More preferably, it is 790 kg / m ^Three It is even more preferable that it is above. From the point of combustibility, 830kg / m ^Three Or less, preferably 820 kg / m ^Three More preferably, it is 815 kg / m ^Three More preferably, it is as follows. In addition, a density represents the density measured by JISK2249 "the density test method of crude oil and petroleum products, and a density / mass / capacity conversion table" here.
[0047]
Moreover, a well-known fuel oil additive can be mix | blended with the kerosene manufactured by the manufacturing method of invention as needed. Known fuel oil additives include, for example, antioxidants, metal deactivators, anti-icing agents, corrosion inhibitors, antistatic agents, colorants, discriminating agents, deodorizing additives and the like. These additives can be used alone or in combination of several kinds. The addition amount can be arbitrarily determined, but the addition amount of each additive is usually 0.2% by mass or less, preferably 0.02% by mass or less, based on the total amount of kerosene.
[0048]
In the kerosene produced by the production method of the invention, the oxidation start temperature is preferably 207 ° C. or higher, more preferably 208 ° C. or higher, and most preferably 209 ° C. or higher from the viewpoint of combustibility. From the viewpoint of stability, the total insoluble content in the storage stability test is desirably 0.3 mg / 100 ml or less, more preferably 0.2 mg / 100 ml or less, and 0.1 mg / 100 ml or less. Most preferred.
[0049]
The kerosene produced by the production method of the invention is preferably used for a petroleum fan heater. This oil fan heater is classified into an open type (indoor intake, indoor exhaust) forced ventilation type heater.
[0050]
The kerosene produced by the production method of the invention is not limited to such an open forced ventilation type heater, but also a semi-enclosed type such as an oil hot water heater, a bath with an oil hot water heater, an oil bath, an oil-fired hot water boiler ( Also used for forced air supply / exhaust type heaters / combustors of closed type (outdoor intake, outdoor exhaust) such as forced ventilation type heaters / combustors for indoor intake and outdoor exhaust), FF type heaters, FF type hot water heaters, etc. Is possible.
[0051]
【Example】
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
Tables 1 to 6 show the main properties of kerosene used as examples and comparative examples. Of the properties shown in the table, those described above were tested by the same method. Others were measured by the following test methods.
[0052]
The flash point was measured by the tag closed flash point test method specified in JIS K 2265 “Crude oil and petroleum products—flash point test method”.
[0053]
The kinematic viscosity was measured by the kinematic viscosity test method specified in JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
[0054]
The peroxide value was measured by the method for measuring the peroxide value specified in JPI-5S-46-96 “Test Method for Peroxide Value of Kerosene”, Petroleum Institute Method.
[0055]
Saybolt was measured by the Saybolt color test method specified in JIS K 2580 “Petroleum products—color test method”.
[0056]
The oxidation start temperature was measured under the following conditions using a high-pressure DSC (model number 27-HT) manufactured by PerkinElmer.
[0057]
<High pressure DSC measurement conditions>
Atmospheric gas: Compressed air
Pressure: 4.0 MPa
Temperature: Initial temperature 50 ° C Temperature increase rate 20 ° C / min Final temperature 500 ° C
[0058]
Further, the total insoluble matter was measured in accordance with ASTM D 2274 “Standard Test Method for Oxidation Stability of Dissolved Fuel Oil (Accelerated Method Insoluble)” according to ASTM D 2274 “Oxidation Stability of Distillate Fuel Oil”. Indicates the minute (2 digits after the decimal point).
[0059]
Table 1 shows the results of using hydrocracked kerosene obtained by hydrocracking with CAT changed to 400 to 416 ° C.
[0060]
[Table 1]

[0061]
As shown in Table 1, when the CAT is 400 ° C., even if it is 100% hydrocracked kerosene (Example 8), there is no problem in properties such as density and flash point, and the oxidation start temperature, total Both insoluble and non-problematic results were obtained. Moreover, even if CAT was 400 degreeC or more, the same result was able to be obtained by mixing with hydrorefining kerosene (Examples 1-7). On the other hand, the base material of 100% hydrocracked kerosene with a CAT of 406 ° C. showed a sufficiently high oxidation start temperature, but the total insoluble content was too much and the quality was not sufficient. In addition, the base material of 100% hydrocracked kerosene with CAT of 413 ° C. and 416 ° C. could not obtain sufficient quality for both the oxidation start temperature and the total insoluble content.
[0062]
Tables 2 and 3 show the results when hydrogenated residue desulfurized kerosene is mixed with hydrorefined kerosene.
[0063]
[Table 2]

[0064]
[Table 3]

[0065]
As shown in Tables 2 and 3 above, each base material composed of 100% by volume of hydrogenated residual oil desulfurized kerosene has problems in terms of oxidation start temperature and total insoluble matter regardless of the end point of distillation, and can be used as a product kerosene. I didn't get it. On the other hand, all the mixed kerosene of Examples 9-21 had sufficient quality. In particular, when the distillation end point of the residual oil desulfurized kerosene was 220 ° C. or less, there was no problem in terms of quality in both the oxidation start temperature and the total insoluble matter even when 4% was mixed (Examples 9 to 11). Further, when the distillation end points were 240 ° C. and 260 ° C., the product kerosene when mixed at 2% satisfied the required qualities for both combustibility and stability (Examples 15 and 16). On the other hand, the mixture of 5% by volume of hydrogenated residual desulfurized kerosene had a problem that the insoluble content was larger than 0.30 even when the distillation end point was 180 ° C. (Comparative Example 1).
[0066]
Tables 4 and 5 show the results of hydrodesulfurization after mixing residual desulfurized kerosene with unwashed kerosene.
[0067]
[Table 4]

[0068]
[Table 5]

[0069]
As shown in the above Tables 4 and 5, the mixed kerosene of Examples 22 to 34 had sufficient quality. In particular, when the distillation end point of the residual oil desulfurized kerosene was 220 ° C. or lower, even if 4% was mixed, there was no problem in quality in terms of oxidation start temperature and total insoluble matter (Examples 22 to 24). In addition, when the distillation end points were 240 ° C. and 260 ° C., the product kerosene mixed with 2% satisfied the required qualities for both combustibility and stability (Examples 28 and 29). On the other hand, a mixture of 5% by volume of residual desulfurized kerosene had a problem that the insoluble content was larger than 0.30 even when the distillation end point was 180 ° C. (Comparative Example 2).
[0070]
Table 6 shows the results when the residual oil desulfurized naphtha wide cut was mixed with crude oil and then distilled with a crude oil distillation apparatus to recover the kerosene fraction.
[0071]
[Table 6]

[0072]
As shown in Table 6 above, the kerosene of Examples 35 to 47 had no quality problems in terms of oxidation start temperature and total insoluble matter, and was comparable to 100% crude oil-derived kerosene. .
[0073]
【The invention's effect】
As described above, according to the present invention, a high-quality product kerosene that is not inferior to the current product kerosene is manufactured using residual oil desulfurized kerosene that has not been used as a product kerosene or hydrocracked kerosene. It becomes possible.

Claims (1)

For hydrocracking one or more selected from vacuum-distilled light oil, catalytic cracking light oil, pyrolysis light oil and degassed oil, obtaining hydrocracked kerosene from which the kerosene fraction was recovered, and hydrorefining kerosene Having the step of mixing the hydrocracked kerosene, the upper limit of the ratio of the total amount of kerosene after mixing of the hydrocracked kerosene,
When the average catalyst temperature (CAT) is 413 ° C. or higher and 416 ° C. or lower, the upper limit is 50% by volume,
When CAT is 406 ° C. or higher and 413 ° C. or lower, the upper limit is the amount calculated by Equation 1 below.
When CAT is 400 ° C. or higher and 406 ° C. or lower , the upper limit is the amount calculated by the following formula 2 (however, when CAT is 400 ° C. or lower, the mixing amount is not limited).
Mixing amount (volume%) = − 2.857 × CAT (° C.) + 1230 (Formula 1)
Mixing amount (volume%) = − 5 × CAT (° C.) + 2100 (Formula 2)
A method for producing kerosene having an oxidation start temperature of 208 ° C. or higher and a total insoluble content of 0.2 mg / 100 ml or lower.