Method for producing bio-jet fuel

Abstract

A method for producing a bio-jet fuel includes a reaction step of hydrogenating, isomerizing, and decomposing a crude oil obtained by a deoxygenation treatment of a raw oil containing a triglyceride and/or a free fatty acid, by using a hydrogenation catalyst and an isomerization catalyst in a hydrogen atmosphere under conditions of a reaction temperature of 180° C. to 350° C. and a pressure of 0.1 MPa to 30 MPa.

Claims

1. A method comprising: obtaining a crude oil by a decarboxylation treatment of a raw oil containing a triglyceride and/or a free fatty acid by using a fat and oil decarboxylation decomposition catalyst comprising any one of magnesium hydroxide, magnesium oxide, and magnesium carbonate, wherein the decarboxylation treatment is performed without supplying hydrogen; and hydrogenating, isomerizing, and decomposing the crude oil by using a hydrogenation catalyst comprising Ni and Pd, and an isomerization catalyst comprising a zeolite in a hydrogen atmosphere under conditions of a reaction temperature in a range of 180° C. to 350° C. and a pressure in a range of 0.1 MPa to 30 MPa to obtain a refined oil.

2. The method according to claim 1, wherein the hydrogenation, isomerization and decomposition are performed by using a hydro-isomerization catalyst comprising the hydrogenation catalyst and the isomerization catalyst.

3. The method according to claim 2, wherein the hydrogenation, isomerization and decomposition are simultaneously performed by using the hydro-isomerization catalyst comprising the hydrogenation catalyst and the isomerization catalyst.

4. The method according to claim 1, wherein the crude oil obtained by the decarboxylation treatment of the raw oil containing a triglyceride and/or a free fatty acid satisfies the following requirements a) to e): a) comprising a hydrocarbon compound having 16 or more carbon atoms; b) having a pour point of −15° C. or more; c) having an aromatic hydrocarbon content rate of 1 to 15 mass %; d) having an acid value of 0 to 20 mg-KOH/g-oil; and e) having a cyclic compound content rate of 15 mass % or lower.

5. The method according to claim 1, wherein the hydrogenation, isomerization and decomposition are performed at 0.5 MPa to 3 MPa.

6. The method according to claim 2, wherein the hydro-isomerization catalyst is a mixed catalyst having a mixing ratio of hydrogenation catalyst:isomerization catalyst of 5:95 to 95:5.

7. The method according to claim 2, wherein the hydro-isomerization catalyst is a composite of the hydrogenation catalyst and the isomerization catalyst.

8. The method according to claim 2, wherein the hydrogenation catalyst is powderized so as to have a particle size smaller than a particle size of the isomerization catalyst, and is attached to or supported on a surface of the isomerization catalyst.

9. The method according to claim 1, wherein the refined oil obtained by hydrogenating, isomerizing, and decomposing the crude oil satisfies the following requirements A) to E): A) comprising 60 mass % or more of a hydrocarbon compound having 9 to 15 carbon atoms; B) having a pour point of −40° C. or lower; C) having an aromatic hydrocarbon content rate of 0.5 mass % or lower; D) having an acid value of 0.015 mg-KOH/g-oil or lower; and E) having a cycloparaffin content rate of 15 mass % or lower.

10. The method according to claim 1, further comprising recovering the obtained refined oil as a bio-jet fuel.

11. The method according to claim 1, further comprising separating a bio-jet fuel from the obtained refined oil.

12. The method according to claim 1, wherein a pour point of the crude oil is −15° C. to 10° C.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 A schematic view of a main section of an apparatus for producing a bio-jet fuel in the present invention is illustrated.

(2) FIG. 2 A composition diagram (C8-9) of products in Examples 1 to 4 is shown.

(3) FIG. 3 The conversion rates in Examples 1 to 4 are shown.

(4) FIG. 4 The pour points of products in Examples 1 to 4 are shown.

(5) FIG. 5 A composition diagram (C8-9) of products in Examples 5 and 6 is shown.

(6) FIG. 6 A composition diagram of products in Examples 5 and 6 is shown.

(7) FIG. 7 The pour points of products in Examples 5 and 6 are shown.

(8) FIG. 8 The selection rates of a product in Example 7 are shown.

(9) FIG. 9 The selection rates of a product in Example 8 are shown.

(10) FIG. 10 The distribution of the number of carbon atoms in a product in Example 9 is shown.

(11) FIG. 11 The distribution of the number of carbon atoms in a product in Example 10 is shown.

(12) FIG. 12 A composition diagram of a product in Example 9 is shown.

(13) FIG. 13 A composition diagram of a product in Example 10 is shown.

DESCRIPTION OF EMBODIMENTS

(14) Hereinafter, an apparatus for producing a bio-jet fuel in the present invention will be described with reference to drawings and specifically described with reference to Examples, but the scope of the present invention is not limited thereto.

(15) FIG. 1 is a schematic view of a main section of an apparatus for producing a bio-jet fuel in the present invention. Reference numeral 1 indicates a hydrogen mass flow controller for controlling the flow rate of hydrogen and maintaining the pressure of a reactor to 0.5 MPa to 3 MPa; reference numeral 2 indicates a raw oil tank for storing the crude oil obtained by decomposing a naturally occurring triglyceride-containing raw oil; reference numeral 3 indicates a transfer pump; reference numeral 3a indicates a preheater for pre-heating a raw oil to 150 to 320° C.; reference numeral 4 indicates a pressure gauge; reference numeral 5 indicates a fixed bed-type reaction vessel for performing hydro-isomerization, and decomposition reactions of a crude oil with a hydro-isomerization catalyst in a hydrogen atmosphere; reference numeral 6 indicates a heater for heating the reaction vessel 5 to 180° C. to 350° C.; reference numeral 7 indicates a hydro-isomerization decomposition catalyst; reference numeral 8 indicates an external temperature controller for measuring the external temperature of a reaction vessel; reference numeral 9 indicates an internal temperature controller for measuring the internal temperature of a reaction vessel; reference numeral 10 indicates a cooler of a reaction product; reference numeral 11 indicates a bio-jet fuel reservoir; reference numeral 12 indicates a pressure holding valve; and reference numeral 13 indicates an outflow portion of a gaseous phase fraction.

(16) The method for producing a bio-jet fuel of the present invention is briefly described in the following by using the apparatus for producing a bio-jet fuel, configured as above.

(17) First, a sealed fixed bed reaction vessel 5 is loaded with a hydro-isomerization decomposition catalyst 7 consisting of a mixture of a hydrogenation catalyst and an isomerization decomposition catalyst, thereby preparing a fixed bed of the hydro-isomerization decomposition catalyst 7. Next, the internal temperature of the fixed bed reaction vessel 5 is heated to around 180 to 350° C. by the heater 6. A hydrogen gas is allowed to flow from the hydrogen gas mass flow controller 1 until the pressure in the reaction vessel reaches 0.5 to 3 MPa. A crude oil for a bio-fuel, while being heated to 150 to 320° C. by the preheater 3a, is transferred by the transfer pump 3 from the raw oil tank 2 to the pre-heated fixed bed reaction vessel 5. A biodiesel fuel is subjected to hydro-isomerization, and decomposition reactions with the superficial velocity in the fixed bed reaction vessel 5 being kept at 0.1 to 10.0 h.sup.−1 at one-stage and converted into a bio-jet fuel. The resulting reaction product is cooled in the cooler 10 and thus subjected to gas-liquid separation. A liquid fraction obtained by such gas-liquid separation is reserved as a crude oil for a bio-jet fuel in a reservoir tank, and a gaseous phase fraction is discharged through the outflow portion 13 toward the outside of the system. The crude oil for a bio-jet fuel is sent to a rectification apparatus not illustrated, and separately flows as a kerosine fraction and is converted into a bio-jet fuel.

EXAMPLES

(18) 1) Raw Material (Crude Oil for Bio-Fuel)

(19) Each sample shown in (Table 2) was used as a raw material.

(20) In (Table 2), “HiBD crude oil” is a crude oil for a bio-fuel, produced based on the description of Japanese Patent No. 5353893.

(21) (1) Examination of Model Compound

(22) A crude oil for a bio-fuel differs in physical properties depending on the raw material composition.

(23) (Table 1) shows oil characteristics of a crude oil for a bio-fuel with respect to each bio raw material. In the Table, “HiBD” is a registered trademark of Kaoru, FUJIMOTO.

(24) TABLE-US-00001 TABLE 1 HiBD (raw HiBD material: (raw material: Test Test items Unit palm oil) waste food oil) method Density at 15° C. g/cm3 0.8172 0.8245 JIS K 2249 Kinetic viscosity mm.sup.2/s 2.812 1.870 JIS K 2283 at 30° C. Flash point ° C. 49.5 47.5 JIS K 2265 (Tag closed cup method) Sulfur content mass 26 34 JIS K 2541 (Ultraviolet ppm fluorescence method) Cetane value — 61.4 55.4 JIS K 2280 Cetane index — 59.5 46.6 JIS K 2280 Pour point ° C. −7.5 −15.0 JIS K 2269 Clogged point ° C. 11 −17 JIS K 2288 10% Carbon — 0.65 0.14 JIS K 2270 residue content Distillation JIS K 2254 properties Initial boiling ° C. 127.5 147.5 — point 5% Distilling ° C. 198.0 167.5 — temperature 10% Distilling ° C. 212.5 174.0 — temperature 20% Distilling ° C. 231.5 191.0 — temperature 30% Distilling ° C. 243.5 205.0 — temperature 40% Distilling ° C. 254.0 218.5 — temperature 50% Distilling ° C. 262.5 233.0 — temperature 60% Distilling ° C. 270.5 247.5 — temperature 70% Distilling ° C. 279.5 261.0 — temperature 80% Distilling ° C. 291.0 275.5 — temperature 90% Distilling ° C. 314.5 289.0 — temperature 95% Distilling ° C. 342.0 301.0 — temperature End point ° C. 345.5 315.0 — Total amount % 97.5 98.0 — distilled Residue % 1.0 1.0 — Amount of loss % 1.5 1.0 — CHO analysis Carbon content mass % 85.2 86.6 ASTM D5291 Hydrogen content mass % 13.6 13.0 ASTM D5291 Oxygen content mass % 1.2 0.4 ASTM D5622 Lower heating kJ/kg 42,000 42,460 JIS K 2279 value (measured value)

(25) Each raw material in “HiBD” in (Table 1) was produced based on the description of Japanese Patent No. 5353893. For evaluating the production method, since it was extremely difficult to analyze the complicated data of the crude oil for a bio-fuel (HiBD) in which a large variety of compounds are mixed, as clear from distillation properties, a bio-jet fuel was produced from a model compound, and the production method was analyzed and evaluated.

(26) (2) Preparation of Model Compound

(27) HiBD (raw material: waste food oil) was subjected to composition analysis and was found to generally include 50% of normal paraffin, 29% of an olefin compound, 10% of an aromatic compound, 7% of an oxygen compound, and 1% of naphthene.

(28) The olefin compound in HiBD was easy to be hydrogenated, thus mixing of the olefin compound merely progressed any reactions other than hydrogenation, caused the results to be complicated, and had no effect on the whole evaluation, and thus the model compound was obtained by excluding the olefin compound and mixing paraffin in an amount corresponding to that of the olefin compound.

(29) The distribution of the number of carbon atoms of the linear hydrocarbon compound in HiBD exhibited peaks at numbers of carbon atoms of 15 and 17, and thus hexadecane having an intermediate number of carbon atoms, between 15 and 17, and heptane were selected for the model compound.

(30) The content rate of an aromatic compound was 0.5% or lower and the content rate of naphthene (cycloparaffin) was 15% or lower, according to ASTM D7566 Annex 2.

(31) The content of naphthene in HiBD is a trace amount and naphthene was mostly produced by hydrogenation of an aromatic compound, and thus the content rate of an aromatic compound in the model compound was set to 20% which exceeds 15%. Toluene was selected for the model of an aromatic compound.

(32) Any free fatty acid would be slightly incorporated into HiBD depending on the production method or the production apparatus. Here, 1% of octanoic acid was allowed to be comprised in the model compound, instead of a free fatty acid.

(33) The composition of the model compound was thus determined to be that of a mixed oil of 50% of n-hexadecane, n-heptane, 29% of toluene, and 1% of octanoic acid, as shown in No. 1 in (Table 2).

(34) TABLE-US-00002 TABLE 2 No. Raw material name Composition 1 Model compound n-hexadecane: 50%, n-heptane: 29%, toluene: 20%, octanoic acid: 1% 2 HiBD crude oil 1 Palm oil as raw material (acid value 6 mg-KOH/mg) 3 HiBD crude oil 2 Waste food oil as raw material (content rate of aromatics 4%) 4 HiBD crude oil 3 Palm oil as raw material (content rate of aromatics 2%)

(35) The compositions shown in (Table 3) were used as hydro-isomerization catalyst.

(36) TABLE-US-00003 TABLE 3a No. Catalyst name Composition 1 Hydrogenation Hydrogenation catalyst Sample-A catalyst 1 manufactured by Nippon Ketjen Co., Ltd. 2 Hydrogenation Hydrogenation catalyst d-2311L catalyst 2 manufactured by Nikko Rica Corporation (Ni: 67.2%, Al: 31.9%, Mo: 0.9%) 3 Isomerization β zeolite preproduction catalyst catalyst 1 F05M-1308-1 manufactured by JGC Catalysts and Chemicals Ltd. 4 Hydrogenation Self-produced Ni—Pd/alumina catalyst catalyst 3 5 Isomerization β-type zeolite catalyst 2 6 Isomerization Y-type zeolite catalyst 3

(37) TABLE-US-00004 TABLE 3b No. Composition 1 Mixed catalyst of hydrogenation catalyst 2 and isomerization catalyst 1 2 Isomerization catalyst attached with 3-wt % Cu-supported hydrogenation catalyst 2 (fine powder) 3 Composite of hydrogenation catalyst 3 and isomerization catalyst 2 4 Composite of hydrogenation catalyst 3 and isomerization catalyst 3

EXAMPLES

(38) A fixed bed reaction vessel was filled with a hydro-isomerization catalyst prepared using a catalyst described in (Table 3a) as described in (Table 3b) by using a raw material having the raw material name described in (Table 2), and an experiment was performed under conditions of (Table 4) under a hydrogen flow at a flow rate of 200 ml/min with the inside of the vessel being kept at a predetermined temperature.

(39) TABLE-US-00005 TABLE 4 Raw Temperature Pressure LHSV No. Label Object of reaction Catalyst material (° C.) (Mpa) (h.sup.−1) 1 Example 1 Isomerization No. 1 Model 220 1.0 0.5 (change of pressure) compound 2 Example 2 No. 1 Model 220 1.5 0.5 compound 3 Example 3 No. 1 Model 220 2.0 0.5 compound 4 Example 4 No. 1 Model 220 0.5 0.5 compound 5 Example 5 Hydro-isomerization No. 2 HiBD 290 2.0 0.5 (crude oil) crude oil 1 6 Example 6 No. 2 HiBD 300 2.0 0.5 crude oil 1 7 Example 7 Isomerization No. 3 Heptane 240 2.0 (change of catalyst) No. 4 8 Example 8 Isomerization No. 3 Heptane 240 2.0 (change of pressure) 9 Example 9 Hydro-isomerization No. 3 HiBD 240 2.0 0.5 (crude oil) crude oil 2 10 Example 10 Hydro-isomerization No. 3 HBD 240 2.0 0.5 (crude oil) crude oil 3

(40) Each product obtained in Examples was evaluated with (1) GC/MS analysis (component distribution of group of peaks in C.sub.8-C.sub.9 zone), (2) GC-FID analysis (conversion rate), and (3) pour point (° C.).

(41) The pour point is here a measurement value obtained by immersing a test tube where 1 ml of a sample was taken, in a Dewar flask where ethanol was placed at a volume of one-fourth of the flask, using a thermometer capable of measuring to −100° C., dropping the temperature at an interval of 5° C. with dry ice and cooling the temperature of such an ethanol solvent by 5° C., then retaining the temperature for 3 minutes, then taking out the test tube and inclining the test tube at an angle, and determining the temperature range between the temperature of the sample which did not cause any flowing (not causing dripping) even in resting for 5 seconds and the sample became a solid state, and the temperature+5° C., as the pour point.

Examples 1 to 4

(42) The pressure dependency of the decomposition reaction was confirmed. A particulate mixed catalyst was used as the hydro-isomerization catalyst with respect to the raw material: model compound, and the pressure dependency of the composition of a bio-jet fuel as a product was confirmed by varying the pressure with the reaction temperature being constantly kept at 220° C. and the LHSV (h.sup.−1) being constantly kept at 0.5. The particulate mixed catalyst here used was one (No. 1 of (Table 3b)) obtained by physically mixing a hydrogenation catalyst d-31 1L manufactured by Nikko Rica Corporation (particle of 2 to 10 mm) as the hydrogenation catalyst and a β zeolite catalyst F05M-1308-1 manufactured by JGC Catalysts and Chemicals Ltd. (pellet of Φ 3.4 mm×3 mm) as the isomerization catalyst at a ratio of about 1:1, by keeping the state of particles.

(43) The confirmation results are shown in (Table 5) to (Table 7) and (FIG. 2) to (FIG. 4).

(44) TABLE-US-00006 TABLE 5 GC/MS analysis: component distribution of group of peaks in C8-C9 zone [%] Example 1 Example 2 Example 3 Example 4 Normal paraffin 7.5 7.8 7.7 7.9 Isoparaffin 68.4 65.2 72.8 70.9 Isoolefin 0 0 0 0 Normal olefin 0 0 0 0 Cycloolefin 0 0 0 0 Naphthene 24.1 27.1 19.5 21.2 Aromatic hydrocarbon 0 0 0 0 Oxygen-containing 0 0 0 0 compound Total 100.0 100.0 100.0 100.0

(45) TABLE-US-00007 TABLE 6 GC-FID: conversion rate [%] Example 1 Example 2 Example 3 Example 4 Heptane −37.3 −43.2 −43.4 −31.0 Toluene 100 100 100 100 Octanoic acid 100 100 100 100 Hexadecane 94.7 98.9 97.5 96.9

(46) TABLE-US-00008 TABLE 7 Pour point Pour point (° C.) Example 1 −50 ~ −45 Example 2 N.D. ~ −65 Detection limit Example 3 N.D. ~ −65 Detection limit Example 4 −55 ~ −50

(47) FIG. 2 is a component distribution diagram of a group of peaks in C8-C9 zone according to GC/MS analysis, FIG. 3 is a conversion rate diagram, and FIG. 4 is a pour point diagram.

(48) As clear from the confirmation results, it was found that a desired reaction proceeded at a low pressure of 0.5 to 2.0 MPa under the conditions of a reaction temperature of 220° C. and a LHSV of 0.5 (h.sup.−1) by using the particulate mixed catalyst as the hydro-isomerization catalyst with respect to the model compound.

Examples 5 and 6

(49) HiBD crude oil 1 as raw material No. 2 in (Table 2) was used as a raw material.

(50) The temperature dependency of the composition of a bio-jet fuel as a product at a high temperature was confirmed in the Examples. The confirmation was performed in the same conditions as in Example 1 except that not only the reaction temperature was varied to 290° C. and 300° C. with the pressure being kept at 2.0 (MPa) and the LHSV being kept at 0.5 (h.sup.−1) as in Example 1, but also the hydro-isomerization catalyst was changed to an attached mixed catalyst (No. 2 of (Table 3b)). The component distribution of HiBD crude oil 1 as raw material No. 2 in (Table 2) was confirmed as that of a control raw material. GC-FID was used for calculation of the component distribution. After sample analysis was performed with GC/MS in the same conditions as in GC-FID, each peak was analyzed. Such each peak as each result in GC-FID measurement was subjected to labelling to normal paraffin or the like based on the GC/MS analysis results. After the labelling, the total peak area per compounds of the same class was determined, and the proportion relative to the whole peak area was defined as the component distribution of each compound.

(51) The confirmation results were shown in (Table 8) to (Table 11) and (FIG. 5) to (FIG. 7).

(52) TABLE-US-00009 TABLE 8 GC/MS analysis: component distribution of group of peaks in C8-C9 zone [%] Raw material Example 5 Example 6 Normal paraffin 45.8 38.7 42.7 Isoparaffin 5.0 33.3 30.6 Isoolefin 0 0 0 Normal olefin 27.7 0 0 Cycloolefin 1.7 0 0 Naphthene 0.7 28.1 26.7 Aromatic hydrocarbon 18.0 0 0 Oxygen-containing compound 0.9 0 0 Total 100.0 100.0 100.0

(53) TABLE-US-00010 TABLE 9 GC-FID: component distribution [%] Raw material Example 5 Example 6 Normal paraffin 80.3 73.3 64.0 Isoparaffin 0.5 16.8 22.8 Olefin compound 10.9 0 0 Naphthene 0.8 9.5 12.6 Aromatic hydrocarbon 3.6 0 0 Oxygen-containing compound 3.9 0.5 0.5 Total 100 100 100

(54) TABLE-US-00011 TABLE 10 Pour point Pour point (° C.) Raw material −30 ~ −25 Example 5 −50 ~ −45 Example 6 −60 ~ −55

(55) TABLE-US-00012 TABLE 11 Distilling temperature (Simulated) [%] Raw material Example 5 Example 6 10% Distilling temperature 190.5 113 93 50% Distilling temperature 254 176 153 90% Distilling temperature 342 245 210.5 End point 575 271 255

(56) As clear from the confirmation results, it was found that raw material No. 2 could be utilized in a high-quality bio-jet fuel under the conditions of use of the attached mixed catalyst as the hydro-isomerization catalyst, a pressure of 2.0 (MPa), and a LHSV of 0.5 (h.sup.−1).

Example 7

(57) [Examination of Isomerization Catalyst]

(58) It is essential for dropping the pour point to isomerize a normal paraffin which is a linear hydrocarbon to an isoparaffin which is a branched hydrocarbon with a methyl group or the like.

(59) In the present evaluation, a test of a model raw material with heptane was introduced so that isomerization activity of each catalyst could be determined by a simple experimental method. The results were classified into the following three reactions, depending on the type of each product, and then evaluated.

(60) 1) Isoheptane was produced (isomerization reaction)

(61) 2) Propane and isobutane were produced (decomposition reaction)

(62) 3) Methane, ethane, normal pentane, and normal hexane were produced (gasification reaction)

(63) Among these reactions, reaction 1) is the most desirable reaction and reaction 2) is the second desirable reaction. On the other hand, reaction 3) is an undesirable reaction because, when the reaction occurs, a gaseous product such as methane is produced and the yield of a refined oil is decreased in an amount corresponding to the production of methane or the like.

(64) The catalyst was a composite (No. 3 and No. 4 of (Table 3b)) of a Ni—Pd/alumina catalyst and a zeolite relatively large in pore size, such as Y or β zeolite, and heptane was used as a model compound. Each reaction was performed at a reaction temperature of 240° C. and a reaction pressure of 2.0 MPa.

(65) The selection rate of each product in the test is shown in Table 12 and FIG. 8.

(66) TABLE-US-00013 TABLE 12 Type of zeolite Selection rate [%] β-type Y-type Gasification 4.8 13.0 Decomposition 17.3 16.9 Isomerization 77.9 70.1 Total 100.0 100.0

(67) It was found as shown in Table 12 and FIG. 8 that not only β-type zeolite, but also Y-type zeolite was excellent as an isomerization catalyst.

Example 8

(68) [Examination of Reaction Pressure]

(69) A comparison evaluation test of activity with respect to the isomerization reaction by varying the reaction pressure was performed.

(70) Heptane was used as a raw material, as in the above. The reaction temperature was 240° C., the pressure was 1.0, 2.0, or 3.0 MPa, and the catalyst here used was a composite of a Ni—Pd/alumina catalyst and zeolite.

(71) The selection rate of each product in the test is shown in Table 13 and FIG. 9.

(72) TABLE-US-00014 TABLE 13 Pressure [Mpa] Selection rate [%] 1.0 2.0 3.0 Gasification 1.9 0.9 0.7 Decomposition 26.6 28.8 26.0 Isomerization 71.4 70.3 73.3 Total 100.0 100.0 100.0

(73) The selection rate in the isomerization reaction being a desirable reaction at any pressure was remarkably high. It was thus found that a sufficient isomerization reaction proceeded even at a low pressure of 1.0 to 3.0 MPa.

Examples 9 and 10

(74) [Characteristics of Refined Oil Obtained from Crude Oil]

(75) Respective crude oils (crude oil 2 and crude oil 3) obtained from waste food oil were used for raw materials, thereby obtaining refined oils at a reaction temperature of 240° C. and at a pressure of 2.0 MPa by the same catalyst as in Example 8.

(76) The resulting refined oils were each subjected to calculation of the distribution of the number of carbon atoms from the GC analysis result, calculation of the component distribution by means of GC/MS, and measurements of the total acid value and the pour point. The respective results of characteristics of the refined oils are shown in Tables 14 to 15 and FIGS. 10 to 13.

(77) TABLE-US-00015 TABLE 14 Example 9 Example 10 Crude Refined Crude Refined Selection rate [%] oil 2 oil oil 3 oil C8 or lower 0.6 23.2 0.2 26.7 C9-15 43.1 67.4 47.4 67.1 C16 or more 56.3 9.3 52.4 6.2

(78) Table 14, and FIG. 10 and FIG. 11 show the distribution of the number of carbon atoms of each of the refined oils. It was found from the results that a C9-15 fraction as a jet fraction was increased in each of Examples 9 and 10.

(79) TABLE-US-00016 TABLE 15 Example 9 Example 10 Component Crude Refined Crude Refined distribution [%] oil 2 oil oil 3 oil Normal paraffin 69.0 26.2 70.8 26.6 Isoparaffin 1.7 63.7 0.3 68.1 Isoolefin 0.0 0.0 0.0 0.0 Normal olefin 11.0 0.0 11.0 0.0 Cycloolefin 0.4 0.0 2.2 0.0 Cycloparaffin 1.5 7.3 4.9 4.4 Aromatics 3.9 0.0 1.6 0.0 Oxygen-containing aromatics 0.2 0.0 0.3 0.0 Oxygen-containing 0.4 0.6 0.9 0.0 cycloparaffin Oxygen-containing 0.1 0.0 0.0 0.0 cycloolefin Oxygen-containing 11.8 2.3 8.0 0.8 linear hydrocarbon Total 100 100 100 100 Cyclic compound [%] 6.5 7.9 9.9 4.4 Aromatic hydrocarbon [%] 4.0 0.0 2.0 0.0 Acid value [mgKOH/g-oil] 0 0 0 0 Pour point [° C.] −10~−5 −50~−45 −10~−5 −55~−50

(80) Table 15 shows the component distribution, acid value and pour point of each of the refined oils, and furthermore FIG. 12 and FIG. 13 each show a component distribution diagram of each of the refined oils. The cyclic compound in Table 15 refers to all cyclic compounds of cycloparaffin, cycloolefin, an aromatic compound, and the like.

(81) The proportions of cycloparaffin and aromatics in each of the refined oils of Example 9 and Example 10 were 7.3% and 0%, and 4.4% and 0%, respectively. The standard values of cycloparaffin and aromatics according to the ASTM standard are a maximum of 15 mass % and a maximum of 0.5 mass %, respectively. Thus, the proportions in Examples 9 and 10 satisfied the standard values. The ASTM standard value defines 0.015 mgKOH/g-oil as the maximum value with respect to the acid value, and the ASTM standard value defines −40° C. with respect to the pour point. As shown in Table 15, the refined oils in Examples 9 and 10 each exhibited an acid value of 0 mgKOH/g-oil, and exhibited a pour point of −50 to −45° C. in Example 9 and a pour point of −55 to −50° C. in Example 10, and thus such acid values and pour points satisfied the ASTM standard values.

INDUSTRIAL APPLICABILITY

(82) The present invention is a significant invention relating to a method for producing a bio-jet fuel, which can provide a high-quality bio-jet fuel at a high yield.

REFERENCE SIGNS LIST

(83) 1 hydrogen mass flow controller 2 raw oil tank 3 transfer pump 4 pressure gauge 5 fixed bed-type reaction vessel 6 heater 7 hydro-isomerization decomposition catalyst layer 8 external temperature controller 9 internal temperature controller 10 cooler 11 bio-jet fuel reservoir 12 pressure holding valve 13 outflow portion