JP2010235944A - Manufacturing method for gasoline base which uses high aromatic hydrocarbon oil as raw material - Google Patents
Manufacturing method for gasoline base which uses high aromatic hydrocarbon oil as raw material Download PDFInfo
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- JP2010235944A JP2010235944A JP2010056650A JP2010056650A JP2010235944A JP 2010235944 A JP2010235944 A JP 2010235944A JP 2010056650 A JP2010056650 A JP 2010056650A JP 2010056650 A JP2010056650 A JP 2010056650A JP 2010235944 A JP2010235944 A JP 2010235944A
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- aromatic
- oil
- aromatic hydrocarbon
- raw material
- hydrocracking
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- 239000003502 gasoline Substances 0.000 title claims abstract description 65
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 53
- 239000002994 raw material Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- 125000003118 aryl group Chemical group 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 55
- 238000005984 hydrogenation reaction Methods 0.000 claims description 51
- 239000003054 catalyst Substances 0.000 claims description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 19
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 230000007423 decrease Effects 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 17
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 9
- 239000003921 oil Substances 0.000 description 95
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 39
- 229910052739 hydrogen Inorganic materials 0.000 description 39
- 239000001257 hydrogen Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 229910021536 Zeolite Inorganic materials 0.000 description 18
- 239000010457 zeolite Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- -1 naphthene hydrocarbon Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 150000001491 aromatic compounds Chemical class 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004231 fluid catalytic cracking Methods 0.000 description 6
- 230000000737 periodic effect Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
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- 238000000354 decomposition reaction Methods 0.000 description 5
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- 239000000295 fuel oil Substances 0.000 description 5
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
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- 238000004939 coking Methods 0.000 description 4
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- 238000005194 fractionation Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
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- 150000002431 hydrogen Chemical class 0.000 description 3
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- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene Chemical class C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- UXNCDAQNSQBHEN-UHFFFAOYSA-N 1,2,3,4-tetrahydrophenanthrene Chemical class C1=CC2=CC=CC=C2C2=C1CCCC2 UXNCDAQNSQBHEN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
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- 150000001239 acenaphthenes Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
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- 150000001454 anthracenes Chemical class 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- 150000001869 cobalt compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
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- 239000002283 diesel fuel Substances 0.000 description 1
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- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、高芳香族炭化水素油を原料とするガソリン基材の製造方法に関し、より詳しくは、分解軽油留分などの高芳香族炭化水素油から、高オクタン価のガソリン基材を効率よく製造することができる方法に関するものである。 The present invention relates to a method for producing a gasoline base material using a highly aromatic hydrocarbon oil as a raw material, and more specifically, efficiently produces a high octane number gasoline base material from a highly aromatic hydrocarbon oil such as a cracked gas oil fraction. It is about how you can do it.
接触分解軽油（ＬＣＯ）などの分解軽油留分は、軽油相当の沸点範囲を有する留分であるものの、芳香族炭化水素が多く含まれているためセタン価が低く、軽油には多くブレンドできない基材である。そのため、主にＡ重油、もしくはＣ重油の希釈材として用いられている。
しかし、最近の重油の需要が低下したことにより、分解軽油留分を有効活用する新しい技術の開発が期待されている。
例えば、分解軽油留分を水素化して、軽油として用いる方法が挙げられる。しかし、この技術は、これまで芳香族炭化水素を水素化してナフテンに転換するものであったため、セタン価がそれほど向上しなかった。したがって、水素化処理に多量の水素を投入してもその水素の消費量に見合った品質改善が図れず、分解軽油の直留軽油への配合割合を高めることができないという問題があった。
一方、近年分解軽油留分に芳香族炭化水素が多く含まれる性質を利用して、一環芳香族炭化水素留分に富むガソリン留分に転換する試みが行なわれてきた。例えば、非特許文献１には、水素化分解装置に分解軽油留分を通油し、水素化・分解して軽質油に転化する方法が開示されている。
しかしながら、これらの水素化分解法では高オクタン価ガソリンを直接製造することができなかったとされている。その理由は、これらの方法は通常高い水素分圧と比較的高い転化レベルで操業されて、芳香族の飽和、無機形態での異種原子の除去およびそれに続く水素化芳香族のパラフィンへの転化が最高になるように運転されてきたからであると、特許文献１（第３〜４頁）に記載されている。
A cracked light oil fraction such as catalytic cracked light oil (LCO) is a fraction having a boiling range equivalent to that of light oil, but has a low cetane number because it contains a large amount of aromatic hydrocarbons, and is a group that cannot be blended with light oil much. It is a material. Therefore, it is mainly used as a diluent for A heavy oil or C heavy oil.
However, due to the recent decrease in demand for heavy oil, the development of new technologies that make effective use of cracked gas oil fractions is expected.
For example, a method of hydrogenating a cracked light oil fraction and using it as light oil can be mentioned. However, this technique has so far been hydrogenated aromatic hydrocarbons to convert them to naphthenes, so the cetane number has not improved so much. Therefore, even if a large amount of hydrogen is added to the hydrotreating process, the quality cannot be improved in accordance with the hydrogen consumption, and there is a problem that the blending ratio of cracked light oil to straight-run gas oil cannot be increased.
On the other hand, in recent years, attempts have been made to convert to a gasoline fraction rich in aromatic hydrocarbon fraction by utilizing the property that cracked gas oil fraction contains a large amount of aromatic hydrocarbons. For example, Non-Patent Document 1 discloses a method in which a cracked light oil fraction is passed through a hydrocracking apparatus, hydrogenated and cracked, and converted to light oil.
However, it is said that high-octane gasoline could not be directly produced by these hydrocracking methods. The reason is that these processes are usually operated at high hydrogen partial pressures and relatively high conversion levels to achieve aromatic saturation, removal of heteroatoms in inorganic form and subsequent conversion of hydrogenated aromatics to paraffins. It is described in Patent Document 1 (pages 3 to 4) that it has been operated so as to be the highest.
このような背景から、この種の開発が種々行われている。
例えば、前記特許文献１では、高オクタン価ガソリンの製造に適した原料油ならびに、水素分圧、分解率についての制御により、少なくとも８７のオクタン価を有するガソリン沸点範囲の生成物を製造する発明が記載されている。この発明において、水素化処理は、水素化処理後無機質の窒素と硫黄とを中間段階で分離すれば、水素化分解装置で触媒のサイクル寿命を延ばすことができるからであるという理由により、有効であるかもしれないと記載されているに過ぎない。
特許文献２では、「ガソリンの沸点以上の温度で沸騰する装入原料（分解軽油相当）を触媒と接触させ、装入原料をガソリン沸点範囲生成物へクラッキングすることからなる高オクタンガソリンの製造方法において、実質上脱アルキル化した装入原料を、水素分圧７ＭＰａ以下、温度３７１〜４８２℃、および１通過当たりのガソリンへの転化率５０％以下で、制御指数２以下をもつゼオライト触媒と接触させる」ことを特徴としている。ここでは、水素化クラッキングする前の水素化処理がガソリンのオクタン価あるいはガソリンの得率等に及ぼす影響についての言及はなく、水素化処理は、水素化処理中に触媒毒の多くを好都合に転化し、かつ水素化処理触媒上に触媒毒を沈着することができること、すなわち水素化クラッキング触媒の寿命を延ばす効果しか期待されていない。
特許文献３では、「重質炭化水素油を精製する第一工程、第一工程で生成したガス中不純物を低減する第二工程、及び第二工程で得られた生成油を水素化分解することにより、少なくとも重質炭化水素油に含まれる沸点２１５℃以上留分の１０容量％以上を２１５℃未満留分に転化し、１環芳香族炭化水素を１０容量％以上含有する水素化分解生成油を得る第三工程を含むアルキルベンゼン類の製造方法」が記載されている。この発明には、「第一工程の処理により、硫黄分は好ましくは５００質量ｐｐｍ以下、窒素分は好ましくは１００質量ｐｐｍ以下に低減され、容量ベースで反応後の全芳香族炭化水素量が反応前の０．５０以上が残存するように制御することがこのましい」と記載されている。しかしながら、例えば、アルキルベンゼン類をより多く得るための第一工程の運転方法についての明確な記載がない。
以上のように、上記のいずれの方法においても、接触分解軽油（ＬＣＯ）などの高芳香族炭化水素油を原料とし、水素化分解等を行い、一環芳香族炭化水素を多く含む有用な留分を得る方法についての技術は、いまだ開示されていない。
したがって、このような、処理が困難な高芳香族炭化水素油を用いる場合であっても、効率よく、有用な留分、例えば高オクタン価のガソリン留分を製造できる技術の出現が求められている。
Against this background, various developments of this kind have been made.
For example, Patent Document 1 describes a feedstock suitable for the production of high-octane gasoline and an invention for producing a gasoline boiling range product having an octane number of at least 87 by controlling hydrogen partial pressure and cracking rate. ing. In this invention, the hydrotreatment is effective because the cycle life of the catalyst can be extended in the hydrocracking apparatus if the inorganic nitrogen and sulfur after the hydrotreatment are separated in an intermediate stage. It is only stated that there may be.
In Patent Document 2, “a process for producing high octane gasoline comprising bringing a charged raw material boiling at a temperature higher than the boiling point of gasoline (equivalent to cracked light oil) into contact with a catalyst and cracking the charged raw material into a gasoline boiling range product. In which a substantially dealkylated charge is brought into contact with a zeolite catalyst having a hydrogen partial pressure of 7 MPa or less, a temperature of 371 to 482 ° C., and a conversion rate to gasoline of 50% or less per pass and a control index of 2 or less. It is characterized by that. Here, there is no mention of the effects of hydrotreatment before hydrocracking on the octane number of gasoline or the yield of gasoline, and hydrotreating conveniently converts most of the catalyst poisons during hydrotreating. In addition, the catalyst poison can be deposited on the hydrotreating catalyst, that is, only the effect of extending the life of the hydrocracking catalyst is expected.
In Patent Document 3, “the first step of refining heavy hydrocarbon oil, the second step of reducing impurities in the gas produced in the first step, and hydrocracking the produced oil obtained in the second step. The hydrocracked product oil containing at least 10% by volume of a fraction having a boiling point of 215 ° C. or higher contained in a heavy hydrocarbon oil is converted into a fraction having a boiling point of 215 ° C. or lower and less than 215 ° C. A process for producing alkylbenzenes comprising a third step to obtain "is described. According to the present invention, “by the treatment in the first step, the sulfur content is preferably reduced to 500 mass ppm or less, the nitrogen content is preferably reduced to 100 mass ppm or less, and the total aromatic hydrocarbon amount after the reaction is reacted on a volume basis. It is preferable to control so that the previous 0.50 or more remains ”. However, for example, there is no clear description about the operation method of the 1st process for obtaining more alkylbenzenes.
As described above, in any of the above methods, a useful fraction containing a large amount of aromatic hydrocarbons is obtained by hydrocracking, etc., using high aromatic hydrocarbon oil such as catalytic cracking light oil (LCO) as a raw material. The technique about how to obtain is not yet disclosed.
Therefore, even when such a highly aromatic hydrocarbon oil that is difficult to process is used, the emergence of a technique capable of efficiently producing a useful fraction, for example, a high-octane gasoline fraction is demanded. .
接触分解軽油（ＬＣＯ）などの高芳香族炭化水素油を原料とし、一環芳香族炭化水素、特に炭素数８の芳香族炭化水素の収率が高い、高オクタン価ガソリン留分を効率的に製造できる方法を提供することを目的とするものである。 Highly aromatic hydrocarbon oils such as catalytic cracking light oil (LCO) can be used as raw materials, and high-octane gasoline fractions with high yields of partially aromatic hydrocarbons, especially C8 aromatic hydrocarbons, can be efficiently produced. It is intended to provide a method.
本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、高芳香族炭化水素油を水素化、次いで水素化分解し、さらに分留する高オクタン価ガソリン留分の製造方法において、水素化工程における反応条件を調整することによって本発明の目的を達成することができることを見出し、この知見に基づいて本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention have provided a method for producing a high-octane gasoline fraction in which a highly aromatic hydrocarbon oil is hydrogenated, then hydrocracked, and further fractionated. It has been found that the object of the present invention can be achieved by adjusting the reaction conditions in the hydrogenation step, and the present invention has been completed based on this finding.
すなわち、本発明は、
［１］高芳香族炭化水素油を原料とし、水素化処理する第一工程、第一工程で得られた生成油を水素化分解処理する第二工程、及び第二工程で得られた分解生成油を分留する第三工程を有するガソリン留分を製造する方法であって、前記水素化処理工程による下記の式（１）で計算される多環芳香族転化率を７０％以上、かつ下記の式（２）で計算される芳香族転化率を２．０％以下となるように、水素化処理条件を調整することを特徴とする高芳香族炭化水素油を原料とするガソリン基材の製造方法、
多環芳香族転化率（％）＝（ａ／ｂ）×１００（％） ・・・（１）
（式中、ａは、水素化工程における多環芳香族濃度の減少幅，ｂは原料中の多環芳香族濃度を示す。）
芳香族転化率（％）＝（Ａ／Ｂ）×１００（％） ・・・（２）
（式中、Ａは、水素化工程における芳香族濃度の減少幅，Ｂは原料中の芳香族濃度を示す。）
［２］水素化処理条件を制御する方法が、反応温度を調整するものである前記［１］に記載の高芳香族炭化水素油を原料とするガソリン基材の製造方法、
［３］水素化分解工程に用いられる水素化分解触媒が、結晶性アルミノシリケートを含み、該結晶性アルミノシリケートのＳｉＯ2／Ａｌ2Ｏ3（モル比）が２０以上、８０以下であることを特徴とする前記［１］又は［２］に記載の高芳香族炭化水素油を原料とするガソリン基材の製造方法、
を提供するものである。
That is, the present invention
[1] Using a highly aromatic hydrocarbon oil as a raw material, a first step of hydrotreating, a second step of hydrocracking the product oil obtained in the first step, and a cracked product obtained in the second step A method for producing a gasoline fraction having a third step of fractionating oil, wherein the polycyclic aromatic conversion calculated by the following formula (1) by the hydrotreating step is 70% or more, and The gasoline base material using a highly aromatic hydrocarbon oil as a raw material, wherein the hydrotreating conditions are adjusted so that the aromatic conversion calculated by the formula (2) is 2.0% or less. Production method,
Polycyclic aromatic conversion (%) = (a / b) × 100 (%) (1)
(In the formula, “a” represents a decrease in the polycyclic aromatic concentration in the hydrogenation step, and “b” represents the polycyclic aromatic concentration in the raw material.)
Aromatic conversion rate (%) = (A / B) × 100 (%) (2)
(In the formula, A represents the reduction range of the aromatic concentration in the hydrogenation step, and B represents the aromatic concentration in the raw material.)
[2] A method for producing a gasoline base material using a highly aromatic hydrocarbon oil as a raw material according to [1] above, wherein the method for controlling the hydrotreating conditions adjusts the reaction temperature,
[3] The hydrocracking catalyst used in the hydrocracking step contains crystalline aluminosilicate, and SiO 2 / Al 2 O 3 (molar ratio) of the crystalline aluminosilicate is 20 or more and 80 or less. A method for producing a gasoline base material using the highly aromatic hydrocarbon oil according to [1] or [2] as a raw material,
Is to provide.
本発明によれば、ＬＣＯなどの高芳香族炭化水素油を原料とし、一環芳香族炭化水素、特に炭素数８の芳香族炭化水素の収率が高い、高オクタン価ガソリン留分を効率的に製造することができる。
また、本発明によれば、圧力・温度が比較的温和な条件で高オクタン価のガソリン留分を製造できるため、省資源・省エネルギーに資する高オクタン価ガソリン留分の製造方法を提供することができる。
また、本発明によれば、高オクタン価を付与するガソリン留分であるとともに、ベンゼン、トルエン、キシレン等の基礎化学原料として有用な炭素数６〜８の芳香族化合物を多く含む留分を提供することができる。
According to the present invention, a high-octane gasoline fraction having a high yield of aromatic hydrocarbons, particularly aromatic hydrocarbons having 8 carbon atoms, can be efficiently produced from high-aromatic hydrocarbon oils such as LCO. can do.
Further, according to the present invention, since a high-octane gasoline fraction can be produced under relatively mild pressure and temperature, a method for producing a high-octane gasoline fraction that contributes to resource saving and energy saving can be provided.
Moreover, according to this invention, while being a gasoline fraction which provides a high octane number, the fraction which contains many C6-C8 aromatic compounds useful as basic chemical raw materials, such as benzene, toluene, xylene, is provided. be able to.
本発明は、高芳香族炭化水素油を原料とし、水素化処理する第一工程、第一工程で得られた生成油を水素化分解処理する第二工程、及び第二工程で得られた分解生成油を分留する第三工程を有するガソリン留分の製造方法である。
本発明において、水素化処理する第一工程と水素化分解処理する第二工程とを必要とするのは、以下のような反応を実施するためである。
すなわち、
（１）まず、水素化処理によって、高芳香族炭化水素油に含まれる各々の多環芳香族炭化水素分子一個について、芳香族環が一個ずつ残るように部分的に水素化し、余分の芳香族環を水素で飽和されたナフテン環に転換する。
（２）次いで、水素化分解処理において、主として、結晶性アルミノシリケート含有触媒の適度な分解作用に基づいて、芳香族環とナフテン環の間のＣ−Ｃ単結合を切断する。これによって、一環芳香族分子一個と飽和炭化水素分子（パラフィンまたはナフテン炭化水素）を生成する。
（３）上記反応機構は、結晶性アルミノシリケートなどの固体酸のプロトンが芳香族環とσ結合を形成し、芳香族環の炭素と芳香族環につながっている炭素の間の単結合をβ切断機構により切断するものと考えられる。（芳香族環内の炭素は二重結合性を帯び強固に結合しているので固体酸では切断されない。）
以下に、それぞれの工程について説明する。
The present invention uses a highly aromatic hydrocarbon oil as a raw material, the first step of hydrotreating, the second step of hydrocracking the product oil obtained in the first step, and the cracking obtained in the second step It is a manufacturing method of the gasoline fraction which has the 3rd process of fractionating produced oil.
In the present invention, the reason why the first step of hydrotreating and the second step of hydrocracking are required is to carry out the following reaction.
That is,
(1) First, by hydrogenation, each polycyclic aromatic hydrocarbon molecule contained in the highly aromatic hydrocarbon oil is partially hydrogenated so that one aromatic ring remains, and excess aromatics are left. The ring is converted to a naphthene ring saturated with hydrogen.
(2) Next, in the hydrocracking treatment, the C—C single bond between the aromatic ring and the naphthene ring is mainly broken based on an appropriate cracking action of the crystalline aluminosilicate-containing catalyst. This produces a single aromatic molecule and a saturated hydrocarbon molecule (paraffin or naphthene hydrocarbon).
(3) The reaction mechanism described above is that a solid acid proton such as crystalline aluminosilicate forms an σ bond with an aromatic ring, and a single bond between the aromatic ring carbon and the carbon connected to the aromatic ring is β It is considered to cut by the cutting mechanism. (The carbon in the aromatic ring has a double bond and is firmly bonded, so it is not cleaved by a solid acid.)
Below, each process is demonstrated.
〔高芳香族炭化水素油〕
本発明における原料としては、高芳香族炭化水素油が用いられる。
高芳香族炭化水素油の芳香族分は、特に制限はないが、芳香族分を５０容量％以上含む炭化水素油であるものが好ましく、６０容量％以上がより好ましく、７０容量％以上がさらに好ましく、８０容量％以上が特に好ましい。このような炭化水素油は、水素化分解によって、オクタン価が高い芳香族化合物を多く含む留分を得るのに有利だからである。一方、高芳香族炭化水素油の芳香族分の上限については、特に制限はないが、苛酷な分解が要求されることによる水素化分解触媒の劣化を抑制する観点から、９５容量％以下のものが好ましい。
なお、ここでいう芳香族炭化水素は、一環、二環、及び三環以上の芳香族炭化水素の合計量である。
一環芳香族炭化水素とは、アルキルベンゼン類の他にアルキルテトラリン類、アルキルインダン類、オクタヒドロアントラセン類、オクタヒドロフェナントレン類なども含まれる。二環芳香族炭化水素とは、ナフタレン類やジヒドロフェナントレン類、ジヒドロアントラセン類、ビフェニル類、フルオレン類、アセナフテン類、テトラヒドロアントラセン類、テトラヒドロフェナントレン類等が該当する。三環以上の芳香族炭化水素とは、フェナントレン類、アントラセン類、ピレン類、フルオランテン類などである。
このような一環、二環、及び三環以上芳香族分の分離・定量は、ＨＰＬＣ分析法によって測定できる。
[Highly aromatic hydrocarbon oil]
A highly aromatic hydrocarbon oil is used as a raw material in the present invention.
The aromatic content of the highly aromatic hydrocarbon oil is not particularly limited, but is preferably a hydrocarbon oil containing an aromatic content of 50% by volume or more, more preferably 60% by volume or more, and further 70% by volume or more. 80% by volume or more is particularly preferable. This is because such a hydrocarbon oil is advantageous for obtaining a fraction containing a large amount of an aromatic compound having a high octane number by hydrocracking. On the other hand, the upper limit of the aromatic content of the highly aromatic hydrocarbon oil is not particularly limited, but it is 95% by volume or less from the viewpoint of suppressing the degradation of the hydrocracking catalyst due to demanding severe cracking. Is preferred.
In addition, the aromatic hydrocarbon here is the total amount of aromatic hydrocarbons of one part, two rings, and three or more rings.
The partially aromatic hydrocarbon includes alkyltetralins, alkylindanes, octahydroanthracenes, octahydrophenanthrenes and the like in addition to alkylbenzenes. Bicyclic aromatic hydrocarbons include naphthalenes, dihydrophenanthrenes, dihydroanthracenes, biphenyls, fluorenes, acenaphthenes, tetrahydroanthracenes, tetrahydrophenanthrenes, and the like. The tricyclic or higher aromatic hydrocarbon includes phenanthrenes, anthracenes, pyrenes, fluoranthenes and the like.
Such separation, quantification of bicyclic, tricyclic and higher aromatic components can be measured by HPLC analysis.
高芳香族炭化水素油の蒸留性状については、水素化分解処理後にガソリン留分を得る必要があることから、ガソリン留分の蒸留性状より高い灯油留分、軽油留分などが好ましく、例えば、エングラー蒸留に基づく１０％点と９０％点が１７０℃〜３９０℃の範囲にあるものが好適であり、１８０〜３８０℃の範囲にあるものがより好適であり、１９０〜３７０℃の範囲にあるものが特に好適である。
このような、高芳香族炭化水素油の具体例としては、例えば、流動接触分解装置（ＦＣＣ），重質油流動接触分解装置（ＲＦＣＣ）またはコーカー等の熱分解装置由来のものや、オイルサンドビチューメンなどのオイルサンド劣質油を起源としたものなどが挙げられる。
Regarding the distillation properties of highly aromatic hydrocarbon oils, since it is necessary to obtain a gasoline fraction after hydrocracking treatment, a kerosene fraction, a light oil fraction, etc. higher than the distillation properties of the gasoline fraction are preferred. Those having 10% point and 90% point based on distillation are in the range of 170 ° C to 390 ° C, more preferably in the range of 180 to 380 ° C, and in the range of 190 to 370 ° C Is particularly preferred.
Specific examples of such highly aromatic hydrocarbon oil include, for example, those derived from a thermal cracking device such as a fluid catalytic cracking device (FCC), a heavy oil fluid catalytic cracking device (RFCC) or a coker, Examples include those derived from inferior oil sands such as bitumen.
その他、高芳香族炭化水素油が有する望ましい性状としては、以下のものが挙げられる。
密度は、通常０．８６〜１．００ｇ／ｃｍ3の範囲のものが好ましく、０．８９〜０．９９、さらには０．９２〜０．９８ｇ／ｃｍ3が好適である。密度が０．８６ｇ／ｃｍ3以上であれば、有効な芳香族炭化水素量を確保することができ、１．００ｇ／ｃｍ3以下であれば、触媒の劣化を抑制することができる。
硫黄分については、通常、０．０２〜４．０質量％のものが好適である。硫黄分が０．０２質量％以上であれば、水素化触媒や水素化分解触媒が還元されて活性が低下することがなく、硫黄分が４．０質量％以下であれば、水素化生成物や水素化分解生成物中に硫黄分が残留する恐れがない。したがって、硫黄分が０．０２質量％未満の場合は、硫化水素、二硫化炭素、ジメチルジスルフィド等の硫黄化合物を添加して使用することが、好ましい。
原料油の窒素分については、２，０００質量ｐｐｍ以下、さらには１，５００質量ｐｐｍ以下、特に１，０００質量ｐｐｍ以下が好適である。また、窒素分の下限については、２０質量ｐｐｍ以上が好ましく、５０質量ｐｐｍ以上がより好ましい。窒素分２０質量ｐｐｍ以上であれば、水素化処理工程において、一環芳香族炭化水素の水素添加が過剰に進行し、開環や飽和環まで進むことが抑制され、また、窒素分が２，０００質量ｐｐｍ以下であれば、触媒活性が低下する恐れがない。
Other desirable properties of the highly aromatic hydrocarbon oil include the following.
The density is preferably in the range of usually 0.86 to 1.00 g / cm 3 , preferably 0.89 to 0.99, and more preferably 0.92 to 0.98 g / cm 3 . When the density is 0.86 g / cm 3 or more, an effective amount of aromatic hydrocarbons can be secured, and when the density is 1.00 g / cm 3 or less, deterioration of the catalyst can be suppressed.
About a sulfur content, the thing of 0.02-4.0 mass% is suitable normally. If the sulfur content is 0.02% by mass or more, the hydrogenation catalyst or hydrocracking catalyst is not reduced and the activity does not decrease. If the sulfur content is 4.0% by mass or less, the hydrogenated product There is no risk of sulfur remaining in the hydrocracking products. Therefore, when the sulfur content is less than 0.02% by mass, it is preferable to add and use a sulfur compound such as hydrogen sulfide, carbon disulfide, or dimethyl disulfide.
The nitrogen content of the raw material oil is preferably 2,000 mass ppm or less, more preferably 1,500 mass ppm or less, and particularly preferably 1,000 mass ppm or less. Moreover, about the lower limit of nitrogen content, 20 mass ppm or more is preferable, and 50 mass ppm or more is more preferable. If the nitrogen content is 20 mass ppm or more, hydrogenation of aromatic hydrocarbons proceeds excessively in the hydrotreating process, and the progress of ring opening or saturation is suppressed, and the nitrogen content is 2,000. If it is less than mass ppm, there is no possibility that catalyst activity will fall.
〔水素化処理：第一工程〕
本発明の第一工程である水素化処理は、前記のとおり、高芳香族炭化水素油に含まれる各々の多環芳香族炭化水素分子一個について、芳香族環が一個ずつ残るように部分的に水素化し、それ以外の芳香族環を水素で飽和されたナフテン環に転換する役割を有する。
この役割を実現するために本発明の水素化処理工程においては、下記の式（１）で計算される多環芳香族転化率を７０％以上、かつ下記の式（２）で計算される芳香族転化率を２．０％以下となるように、水素化処理条件を調整する。芳香族転化率は好ましくは１．０％以下に調整する。
多環芳香族転化率（％）＝（ａ／ｂ）×１００（％） ・・・（１）
（式中、ａは、水素化工程における多環芳香族濃度の減少幅，ｂは原料中の多環芳香族濃度を示す。）
芳香族転化率（％）＝（Ａ／Ｂ）×１００（％） ・・・（２）
（式中、Ａは、水素化工程における芳香族濃度の減少幅，Ｂは原料中の芳香族濃度を示す。）
このように水素化処理反応を調整することによって、目的とする多環芳香族炭化水素分子一個について、芳香族環が一個ずつ残るように部分的に水素化し、それ以外の芳香族環を水素で飽和されたナフテン環に転換することができる。
[Hydrogenation treatment: First step]
As described above, the hydrogenation treatment that is the first step of the present invention is partially performed so that one aromatic ring remains for each polycyclic aromatic hydrocarbon molecule contained in the highly aromatic hydrocarbon oil. It has the role of hydrogenating and converting other aromatic rings to naphthene rings saturated with hydrogen.
In order to realize this role, in the hydrotreating process of the present invention, the polycyclic aromatic conversion rate calculated by the following formula (1) is 70% or more and the fragrance calculated by the following formula (2). The hydrotreating conditions are adjusted so that the group conversion is 2.0% or less. The aromatic conversion rate is preferably adjusted to 1.0% or less.
Polycyclic aromatic conversion (%) = (a / b) × 100 (%) (1)
(In the formula, “a” represents a decrease in the polycyclic aromatic concentration in the hydrogenation step, and “b” represents the polycyclic aromatic concentration in the raw material.)
Aromatic conversion rate (%) = (A / B) × 100 (%) (2)
(In the formula, A represents the reduction range of the aromatic concentration in the hydrogenation step, and B represents the aromatic concentration in the raw material.)
By adjusting the hydrotreating reaction in this way, one target polycyclic aromatic hydrocarbon molecule is partially hydrogenated so that one aromatic ring remains at a time, and other aromatic rings are hydrogenated. It can be converted to a saturated naphthene ring.
水素化処理反応を調整する水素化処理は、以下の（ｉ）〜（iv）を満たす条件下で実施するのが好ましい（括弧内は、より好ましい範囲である）。
（ｉ）反応温度：２５０〜４２０℃（２８０〜４００℃）
なお、ここでいう反応温度は、重量平均温度（ＷＡＴ）である。
（ii）水素分圧：５〜１５ＭＰａ（６〜１２ＭＰａ）
（iii）水素／油比：３００〜３，０００Ｎｍ3／ｋｌ（５００〜２，０００Ｎｍ3／ｋｌ）
（iv）液空間速度（ＬＨＳＶ）：０．２〜３．０ｈ-1（０．３〜２．５ｈ-1）
このような条件で水素化処理反応を行えば、目的に近い性状を有する水素化生成物を得ることができる。
The hydrogenation treatment for adjusting the hydrotreatment reaction is preferably carried out under the conditions satisfying the following (i) to (iv) (the parentheses are more preferred ranges).
(I) Reaction temperature: 250-420 ° C (280-400 ° C)
In addition, the reaction temperature here is a weight average temperature (WAT).
(Ii) Hydrogen partial pressure: 5 to 15 MPa (6 to 12 MPa)
(Iii) Hydrogen / oil ratio: 300 to 3,000 Nm 3 / kl (500 to 2,000 Nm 3 / kl)
(Iv) Liquid hourly space velocity (LHSV): 0.2 to 3.0 h −1 (0.3 to 2.5 h −1 )
When the hydrotreating reaction is performed under such conditions, a hydrogenated product having properties close to the intended purpose can be obtained.
本発明においては、上記の条件の中で、さらに式（１）、式（２）を確実に、連続的に満たし、多環芳香族転化率を高く、芳香族転化率を低く保つために水素化処理条件を調整する。調整は、上記（ｉ）〜（iv）の中の１の条件又は２以上の条件を組合せて行う。例えば、調整の効果が大きく、かつ調整操作が容易である観点から、（ｉ）の反応温度を調整することが好適な手段である。
反応温度が２５０〜４２０℃であれば、二環以上の多環芳香族炭化水素の芳香族環を１個残す部分水素化反応が良好に進行し、水素化分解工程入口の反応温度が低下し水素化分解工程における分解率が上がらない恐れも無い。
水素分圧が５〜１５ＭＰａであれば、前記部分水素化反応で必要な水素量及びクエンチに必要な水素量が反応系内に確保でき、芳香族転化率が高くなりすぎる等の過剰な水素化が進行したり、水素化触媒がコーキング劣化する恐れが無い。
水素／油比は、３００〜３，０００Ｎｍ3／ｋｌであれば、水素化処理に必要な水素量、触媒の冷却に必要な水素量を適切に確保でき、また経済性も確保できる。
液空間速度（ＬＨＳＶ）が０．２〜３．０ｈ-1であれば、前記良好な反応温度を保つことができる。
In the present invention, hydrogen is used in order to ensure that the formulas (1) and (2) are continuously satisfied, the polycyclic aromatic conversion rate is high, and the aromatic conversion rate is kept low. Adjust the processing conditions. The adjustment is performed by combining one condition or two or more conditions among the above (i) to (iv). For example, from the viewpoint that the effect of adjustment is large and the adjustment operation is easy, it is preferable to adjust the reaction temperature of (i).
If the reaction temperature is 250 to 420 ° C., the partial hydrogenation reaction that leaves one aromatic ring of two or more polycyclic aromatic hydrocarbons proceeds well, and the reaction temperature at the hydrocracking process inlet decreases. There is no fear that the decomposition rate in the hydrocracking process will not increase.
If the hydrogen partial pressure is 5 to 15 MPa, the amount of hydrogen necessary for the partial hydrogenation reaction and the amount of hydrogen necessary for quenching can be secured in the reaction system, and excessive hydrogenation such as the aromatic conversion rate becomes too high. There is no risk that the hydrogenation catalyst will progress or coking will deteriorate.
Hydrogen / oil ratio, if 300~3,000Nm 3 / kl, the amount of hydrogen required for the hydrogenation process, suitably secured amount of hydrogen required for the cooling of the catalyst, also can be secured also economical.
When the liquid hourly space velocity (LHSV) is 0.2 to 3.0 h −1 , the good reaction temperature can be maintained.
多環芳香族転化率が７０％未満の場合、もしくはより高くしたい場合は、前記範囲内で反応温度を調整する。通常は、反応温度を高めると多環芳香族転化率が高くなる方向に反応が進む。原料油の組成にも影響されるが、多環芳香族の水素化反応の平衡制約のため、反応温度を高めると多環芳香族転化率がかえって低くなることも有るが、このような場合には反応温度を下げる方向で調整する。
また、多環芳香族転化率を高めるためには、水素化反応を進行させるため、水素分圧や水素／油比を調整することも可能である。通常、水素分圧や水素／油比は高める方向で調整するが、原料油の気液の状態によっては、水素／油比を上げるとかえって水素化反応が抑制されることがあり、このような場合には水素／油比を下げる方向で調整する。
多環芳香族転化率を高くしすぎると過剰な水素化反応が進み、芳香族転化率が２．０％を超える場合が有る。その場合、又は芳香族転化率が２．０％以内であるが、より低くしたい場合、通常は前記範囲内で反応温度や水素分圧を下げる方向で調整する。原料油の気液の状態によっては水素／油比を上げるとかえって水素化反応が抑制されることも有るが、このような場合には水素／油比を下げる方向で調整する。
反応温度や水素分圧、水素／油比を調整し難い場合は、液空間速度（ＬＨＳＶ）を高くすると、多環芳香族転化率や芳香族転化率は小さくなり、低くすると両転化率とも高くなる方向に反応が進む。
以上の調整を連続的に行うときは、水素化処理の入り口と出口における油の性状（例えば、密度、動粘度、液体クロマト分析値など）を連続的に監視し、多環芳香族転化率及び芳香族転化率の変化を解析するシステムを有することが好ましい。
When the polycyclic aromatic conversion is less than 70% or higher, the reaction temperature is adjusted within the above range. Usually, when the reaction temperature is raised, the reaction proceeds in the direction of increasing the polycyclic aromatic conversion rate. Although it is affected by the composition of the feedstock, due to the equilibrium limitation of the polycyclic aromatic hydrogenation reaction, if the reaction temperature is increased, the polycyclic aromatic conversion rate may be lowered. Is adjusted to lower the reaction temperature.
Further, in order to increase the polycyclic aromatic conversion, it is possible to adjust the hydrogen partial pressure and the hydrogen / oil ratio in order to advance the hydrogenation reaction. Usually, the hydrogen partial pressure and the hydrogen / oil ratio are adjusted in the direction of increasing, but depending on the gas-liquid state of the feedstock oil, the hydrogenation reaction may be suppressed by increasing the hydrogen / oil ratio. If this is the case, adjust the hydrogen / oil ratio.
If the polycyclic aromatic conversion rate is too high, an excessive hydrogenation reaction proceeds, and the aromatic conversion rate may exceed 2.0%. In that case, or the aromatic conversion rate is within 2.0%, but when it is desired to lower it, the reaction temperature and the hydrogen partial pressure are usually adjusted within the above ranges. Depending on the gas-liquid state of the feedstock, increasing the hydrogen / oil ratio may suppress the hydrogenation reaction. In such a case, the hydrogen / oil ratio is adjusted to decrease.
If it is difficult to adjust the reaction temperature, hydrogen partial pressure, and hydrogen / oil ratio, increasing the liquid space velocity (LHSV) decreases the polycyclic aromatic conversion rate and aromatic conversion rate, and decreasing it increases both conversion rates. The reaction proceeds in this direction.
When the above adjustments are made continuously, the properties of the oil (eg, density, kinematic viscosity, liquid chromatographic analysis value, etc.) at the inlet and outlet of the hydrotreatment are continuously monitored, and the polycyclic aromatic conversion rate and It is preferable to have a system for analyzing changes in aromatic conversion.
本発明に用いる水素化触媒としては，通常周期表第６、８、９、１０族金属のうちの少なくとも一種の水素化活性金属成分を耐火性無機酸化物担体に担持した触媒を用いる。
水素化活性金属成分としては、例えば、モリブデン、タングステン、コバルト、ニッケル等が好適である。モリブデン化合物としては三酸化モリブデン、モリブデン酸アンモニウム等が好ましく、タングステン化合物としては、三酸化タングステン、タングステン酸アンモニウム等が好ましい。コバルト化合物としては、炭酸コバルト、塩基性炭酸コバルト、硝酸コバルト等が好ましく、ニッケル化合物としては、炭酸ニッケル、塩基性炭酸ニッケル、硝酸ニッケル等が好ましい。さらに、リン化合物を担持させることができ、このリン化合物としては、五酸化リン、正リン酸等の各種リン酸が使用される。担持量は触媒体として、酸化物基準で、モリブデン、タングステンが１０〜４０質量％、コバルト、ニッケルが１〜１０質量％、リンが１〜１０質量％が好適である。
中でも、水素化活性金属成分としてモリブデン、コバルト、ニッケルのうちの少なくとも一種、特にモリブデンとニッケル、もしくはモリブデンとコバルトを組合せたものが好ましい。
As the hydrogenation catalyst used in the present invention, a catalyst in which at least one hydrogenation active metal component of metals in Groups 6, 8, 9, and 10 of the periodic table is supported on a refractory inorganic oxide carrier is usually used.
As the hydrogenation active metal component, for example, molybdenum, tungsten, cobalt, nickel and the like are suitable. As the molybdenum compound, molybdenum trioxide, ammonium molybdate and the like are preferable, and as the tungsten compound, tungsten trioxide, ammonium tungstate and the like are preferable. As the cobalt compound, cobalt carbonate, basic cobalt carbonate, cobalt nitrate and the like are preferable, and as the nickel compound, nickel carbonate, basic nickel carbonate, nickel nitrate and the like are preferable. Further, a phosphorus compound can be supported, and various phosphoric acids such as phosphorus pentoxide and orthophosphoric acid are used as the phosphorus compound. The supported amount of the catalyst body is preferably 10 to 40% by mass of molybdenum and tungsten, 1 to 10% by mass of cobalt and nickel, and 1 to 10% by mass of phosphorus on the oxide basis.
Among them, the hydrogenation active metal component is preferably at least one of molybdenum, cobalt, and nickel, particularly a combination of molybdenum and nickel, or molybdenum and cobalt.
前記耐火性無機酸化物としては、特に制限はないが、アルミナ、シリカ−アルミナ、シリカ−ボリア、アルミナ−ボリア、粘土鉱物及びそれらの混合物等が好適に使用される。これらの中でも、アルミナ、シリカ−アルミナが好適である。ただし、ここでいうシリカ−アルミナは、ハイアルミナやロウアルミナの名称で呼ばれる強い固体酸性をもつものではなく、シリカ−アルミナに含まれるシリカの含有量が５０質量％以下、好ましくは３０質量％以下、特に好ましくは２０質量％以下のもので、強い固体酸性をもたないものを使用する。なお、上記水素化触媒は，公知の方法で製造することができる。 The refractory inorganic oxide is not particularly limited, and alumina, silica-alumina, silica-boria, alumina-boria, clay mineral, and mixtures thereof are preferably used. Among these, alumina and silica-alumina are preferable. However, the silica-alumina here does not have strong solid acidity called high alumina or wax alumina, and the silica content in the silica-alumina is 50% by mass or less, preferably 30% by mass or less. Particularly preferably, 20% by mass or less, and no strong solid acidity is used. In addition, the said hydrogenation catalyst can be manufactured by a well-known method.
〔水素化分解処理：第二工程〕
本発明の第二工程である水素化分解処理は、前記のとおり、主として、結晶性アルミノシリケート含有触媒の適度な分解作用に基づいて、芳香族環とナフテン環の間のＣ−Ｃ単結合を切断する役割を有する。これによって、一環芳香族分子一個と飽和炭化水素分子（パラフィンまたはナフテン炭化水素）を生成するものである。
この役割を実現するために本発明の水素化分解処理工程においては、以下のような条件で水素化分解反応を行う。
例えば、以下の（V）〜（VIII）を満たす条件下で実施するのが好ましい（括弧内は、より好ましい範囲である）。
（V）反応温度：３２０〜４４０℃（３３０〜４３０℃）
（VI）水素分圧：５〜１５ＭＰａ（６〜１２ＭＰａ）
（VII）水素／油比：１，０００〜３，０００Ｎｍ3／ｋｌ
（VIII）液空間速度（ＬＨＳＶ）：０．３〜３．０ｈ-1
このような条件で水素化分解反応を行えば、芳香族環とナフテン環の間のＣ−Ｃ単結合を切断し、一環芳香族分子一個と飽和炭化水素分子を生成することができる。
[Hydrolysis treatment: Second step]
As described above, the hydrocracking treatment, which is the second step of the present invention, mainly forms a C—C single bond between an aromatic ring and a naphthene ring based on an appropriate cracking action of the crystalline aluminosilicate-containing catalyst. Has the role of cutting. Thereby, one aromatic molecule and saturated hydrocarbon molecule (paraffin or naphthene hydrocarbon) are produced.
In order to realize this role, in the hydrocracking process of the present invention, the hydrocracking reaction is performed under the following conditions.
For example, it is preferable to carry out under the conditions satisfying the following (V) to (VIII) (the parenthesized values are more preferable ranges).
(V) Reaction temperature: 320 to 440 ° C (330 to 430 ° C)
(VI) Hydrogen partial pressure: 5 to 15 MPa (6 to 12 MPa)
(VII) a hydrogen / oil ratio: 1,000~3,000Nm 3 / kl
(VIII) Liquid space velocity (LHSV): 0.3 to 3.0 h −1
If the hydrogenolysis reaction is performed under such conditions, a single C—C bond between the aromatic ring and the naphthene ring can be cleaved to produce one aromatic molecule and a saturated hydrocarbon molecule.
反応温度が低いと分解率が低すぎ、目的とするガソリン基材の収率を高めることができない。反応温度が高いと過分解状態となり、ロスが発生するのみならず、水素化分解触媒の劣化が顕著になるため好ましくない。
水素分圧や水素／油比がこの範囲であると水素化分解やクエンチに必要な水素量を確保でき、触媒のコーキング劣化を防ぎつつ、水素化分解が進みすぎることも抑制できる。
液空間速度（ＬＨＳＶ）が低すぎると、水素化分解工程においても過剰な水素化、すなわち、処理後の油中の一環芳香族含有量が少なくなる恐れが有る。ＬＨＳＶが高すぎると分解率を調整するために反応温度が高くなりすぎ、コーキング劣化を招くため好ましくない。
If the reaction temperature is low, the decomposition rate is too low, and the yield of the target gasoline base material cannot be increased. If the reaction temperature is high, it will be in an over-decomposition state, which not only causes loss but also undesirably deteriorates the hydrocracking catalyst.
When the hydrogen partial pressure and the hydrogen / oil ratio are within this range, the amount of hydrogen necessary for hydrocracking and quenching can be secured, and the excessive progress of hydrocracking can be suppressed while preventing coking deterioration of the catalyst.
If the liquid space velocity (LHSV) is too low, excessive hydrogenation in the hydrocracking process, that is, the partial aromatic content in the treated oil may be reduced. If the LHSV is too high, the reaction temperature becomes too high to adjust the decomposition rate, which leads to coking deterioration.
水素化分解処理における水素化分解触媒としては、ＳｉＯ2／Ａｌ2Ｏ3（モル比）が２０以上８０以下の結晶性アルミノシリケートを含む耐火性無機酸化物からなる担体に、活性金属を担持した触媒を用いることが好ましい。
前記耐火性無機酸化物のうちＳｉＯ2／Ａｌ2Ｏ3（モル比）が２０以上８０以下の結晶性アルミノシリケートを除く耐火性無機酸化物としては、例えば、アルミナ、シリカ−アルミナ、シリカ−ボリア、アルミナ−ボリア、粘土鉱物などが挙げられ、通常これらから選ばれる１種以上を用いる。
一方、ＳｉＯ2／Ａｌ2Ｏ3（モル比）が２０以上８０以下の結晶性アルミノシリケートとしては、β型ゼオライトや超安定Ｙ型ゼオライトが好ましく、特に超安定Ｙ型ゼオライトが好ましい。
As a hydrocracking catalyst in the hydrocracking treatment, an active metal is supported on a support made of a refractory inorganic oxide containing a crystalline aluminosilicate having a SiO 2 / Al 2 O 3 (molar ratio) of 20 to 80. It is preferable to use a catalyst.
Examples of the refractory inorganic oxide excluding the crystalline aluminosilicate having a SiO 2 / Al 2 O 3 (molar ratio) of 20 to 80 in the refractory inorganic oxide include, for example, alumina, silica-alumina, silica-boria. , Alumina-boria, clay mineral and the like, and usually one or more selected from these are used.
On the other hand, the crystalline aluminosilicate of the SiO 2 / Al 2 O 3 (molar ratio) of 20 to 80., beta type zeolite and ultrastable Y-type zeolite is preferred, especially ultrastable Y-type zeolite is preferred.
前記超安定Ｙ型ゼオライトとしては、ＳｉＯ2／Ａｌ2Ｏ3（モル比）が２５以上で、格子定数が２．４４０ｎｍ以下、及び結晶化度が５０％以上の条件を満たすものが好適である。
中でも、酸量が０．２ｍｍｏｌ／ｇ以上のものが好ましい。酸量は、アンモニアＴＰＤ法により測定した値である。
このような、超安定Ｙ型ゼオライトは、水素化分解反応において、コーキング劣化を生ずることがなく、良好な分解反応を行うことができる。
このような超安定Ｙ型ゼオライトの製造方法は、通常Y型ゼオライトを水蒸気下にてスチーミング処理し、次いで酸処理を行う方法が好適である。この場合、スチーミング処理は５４０〜８１０℃で行い、酸処理は、硫酸、硝酸、塩酸などの鉱酸を加えて、脱アルミニウムおよび脱落アルミニウムの洗浄を行う方法が好ましい。この酸処理において、遷移金属の酸性塩を加えて、ゼオライトを修飾することができる。その中で、鉄の硫酸塩または硝酸塩を加えて混合攪拌することにより、鉄の担持ならびに脱アルミニウムおよび脱落アルミニウムの洗浄をおこなってもよい。
As the ultrastable Y-type zeolite, those satisfying the conditions that SiO 2 / Al 2 O 3 (molar ratio) is 25 or more, the lattice constant is 2.440 nm or less, and the crystallinity is 50% or more are suitable. .
Among them, those having an acid amount of 0.2 mmol / g or more are preferable. The acid amount is a value measured by an ammonia TPD method.
Such an ultrastable Y-type zeolite does not cause coking deterioration in the hydrocracking reaction and can perform a good cracking reaction.
As a method for producing such an ultra-stable Y-type zeolite, a method is generally preferred in which the Y-type zeolite is steamed under steam and then acid-treated. In this case, the steaming treatment is preferably performed at 540 to 810 ° C., and the acid treatment is preferably performed by adding a mineral acid such as sulfuric acid, nitric acid or hydrochloric acid to wash the dealuminated aluminum and the dropped aluminum. In this acid treatment, the zeolite can be modified by adding an acid salt of a transition metal. Among these, iron sulfate and nitrate may be washed by adding iron sulfate or nitrate and mixing and stirring.
耐火性無機酸化物担体中における、前記ＳｉＯ2／Ａｌ2Ｏ3（モル比）が２０以上８０以下の結晶性アルミノシリケートの含有割合は、結晶性アルミノシリケートが２０〜８０質量％であることが好ましく、３０〜７５質量％であることがより好ましい。耐火性無機酸化物担体中における結晶性アルミノシリケートの含有割合が２０質量％以上であることによって、適切な水素化分解能を得ることができ、結晶性アルミノシリケートの含有割合が８０質量％以下であれば、過分解を抑制できる。
結晶性アルミノシリケートの含有割合は、４０〜７０質量％であることがより好ましい。
The content ratio of the crystalline aluminosilicate having a SiO 2 / Al 2 O 3 (molar ratio) of 20 or more and 80 or less in the refractory inorganic oxide carrier is that the crystalline aluminosilicate is 20 to 80% by mass. Preferably, it is 30-75 mass%. When the content ratio of the crystalline aluminosilicate in the refractory inorganic oxide support is 20% by mass or more, an appropriate hydrogenation resolution can be obtained, and the content ratio of the crystalline aluminosilicate is 80% by mass or less. In this case, excessive decomposition can be suppressed.
The content ratio of the crystalline aluminosilicate is more preferably 40 to 70% by mass.
水素化分解触媒は、上記担体に、周期表第６族、第８族、第９族、及び第１０族金属のうちの少なくとも一種の活性金属を担持したものが好ましい。特に、周期表第６族金属及び第８〜１０族金属をそれぞれ少なくとも一種を担持したものが好ましい。周期表第６族金属として、モリブデン，タングステンが好適に挙げられ、特にモリブデンが好ましい。また、周期表第８〜１０族の金属としては、コバルト又はニッケルが挙げられる。
これらの金属の担持量は、周期表第６族金属の場合は、通常金属酸化物として触媒基準で、３〜４０質量％、さらに好ましくは５〜３５質量％である。第８〜１０族金属の場合は、通常１〜１５質量％、さらに好ましくは２〜１０質量％である。
The hydrocracking catalyst is preferably a catalyst in which at least one active metal selected from Group 6, Group 8, Group 9, and Group 10 metals of the periodic table is supported on the support. In particular, it is preferable to carry at least one group 6 metal and group 8 to 10 metal of the periodic table. As the Group 6 metal of the periodic table, molybdenum and tungsten are preferably exemplified, and molybdenum is particularly preferable. Moreover, cobalt or nickel is mentioned as a group 8-10 metal of a periodic table.
In the case of a Group 6 metal of the periodic table, the supported amount of these metals is usually 3 to 40% by mass, more preferably 5 to 35% by mass, based on the catalyst as a metal oxide. In the case of a Group 8-10 metal, it is usually 1-15% by mass, more preferably 2-10% by mass.
［分留工程：第三工程］
本発明の第三工程である分留工程は、前記第二工程で得られた分解生成油を分留し、例えば、ガス、ＬＰＧ、軽質ガソリン、重質ガソリン、灯軽油留分等に分留する。これらの分留は、それぞれの沸点範囲によって、通常の方法で分留すればよい。
例えば、重質ガソリン留分をガソリンに適用するにはベンゼンが含まれない方が好適であることから、ベンゼンの沸点８０℃以上で分留することがある。またベンゼンが含まれるように重質ガソリン留分を分留し、次いで蒸留により脱ベンゼン処理することもある。重質ガソリン留分を、ガスクロ蒸留の終点が１８０〜２１０℃となるように分留すると、炭素数７、８、９の芳香族炭化水素が濃縮されるため、オクタン価が高くガソリンとして好適である。該留分を精密蒸留して、炭素数７、８の留分、すなわち、トルエン、キシレン類を得る場合、ガスクロ蒸留の終点をより低く設定することが好適である。
[Fractionation process: Third process]
The fractionation step, which is the third step of the present invention, fractionates the cracked product oil obtained in the second step, for example, fractionation into gas, LPG, light gasoline, heavy gasoline, kerosene oil fraction, etc. To do. These fractions may be fractionated by a usual method depending on the respective boiling range.
For example, in order to apply a heavy gasoline fraction to gasoline, it is preferable that benzene is not contained, and therefore fractionation may occur at a boiling point of 80 ° C. or higher of benzene. Further, a heavy gasoline fraction may be fractionated so that benzene is contained, and then debenzene-treated by distillation. When heavy gasoline fractions are fractionally distilled so that the end point of gas chromatography is 180 to 210 ° C., aromatic hydrocarbons having 7, 8, and 9 carbon atoms are concentrated, so that the octane number is high and suitable as gasoline. . When the fraction is subjected to precision distillation to obtain a fraction having 7 or 8 carbon atoms, that is, toluene or xylenes, it is preferable to set the end point of gas chromatography distillation to be lower.
以上のようにして得られる重質ガソリン基材は、高オクタンであって、本発明が目的とするものである。また、この留分は、炭素数６〜８の芳香族化合物、特に炭素数８の芳香族化合物を多量に含む留分である。したがって、それらを基礎化学原料として有用な炭素数６〜８の芳香族化合物としても利用できる。
なお、得られた重質ガソリン基材を白金／アルミナ系の改質触媒を用いて脱水素することにより、重質ガソリン基材に含まれる炭素数７〜９のナフテン炭化水素を、炭素数７〜９の芳香族炭化水素に転換することも可能である。この場合においても、本発明により芳香族炭化水素とナフテン炭化水素の比率が高く維持されるので、脱水素塔の能力、負荷を低減することができ有利である。
このような条件に調整して水素化を行うことによって、得られるガソリン基材のオクタン価が高く、重質ガソリン基材に含まれる一環芳香族とＣ８芳香族の収率をより高く維持することができる。
The heavy gasoline base material obtained as described above has a high octane and is the object of the present invention. Further, this fraction is a fraction containing a large amount of an aromatic compound having 6 to 8 carbon atoms, particularly an aromatic compound having 8 carbon atoms. Therefore, they can be used as aromatic compounds having 6 to 8 carbon atoms that are useful as basic chemical raw materials.
In addition, by dehydrogenating the obtained heavy gasoline base material using a platinum / alumina-based reforming catalyst, the naphthene hydrocarbon having 7 to 9 carbon atoms contained in the heavy gasoline base material is converted to carbon number 7 It is also possible to convert to -9 aromatic hydrocarbons. Even in this case, the ratio of the aromatic hydrocarbon and the naphthene hydrocarbon is maintained high according to the present invention, which is advantageous in that the capacity and load of the dehydrogenation tower can be reduced.
By adjusting to such conditions and performing hydrogenation, the octane number of the obtained gasoline base material is high, and the yield of the partial aromatics and C8 aromatics contained in the heavy gasoline base material can be maintained higher. it can.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。なお、実施例の各分析法は、表１に記載の方法で行った。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. In addition, each analysis method of an Example was performed by the method of Table 1.
［原料油］
表２に示す性状を有する分解軽油を用いた。ＬＣＯ−１は、重質油流動接触分解（ＲＦＣＣ）装置から得られた分解軽油、ＬＣＯ−２は流動接触分解（ＦＣＣ）装置から得られた分解軽油である。本文中に記載の無い、実施例及び比較例の評価項目の測定方法は表１に示す。
[Raw oil]
A cracked light oil having the properties shown in Table 2 was used. LCO-1 is a cracked light oil obtained from a heavy oil fluid catalytic cracking (RFCC) device, and LCO-2 is a cracked light oil obtained from a fluid catalytic cracking (FCC) device. Table 1 shows the measurement methods of the evaluation items of Examples and Comparative Examples that are not described in the text.
［水素化触媒の調製］
国際公開特許ＷＯ２００２／０４９９６３に基づき、チタン含有水溶液を調製した。５００℃で４時間焼成することにより求めたチタン酸化物（ＴｉＯ2）の割合が８５質量％である含水酸化チタン粉末１２．７ｇと７０ｇの純水を、内容積１Ｌのガラス製ビーカーに入れ、攪拌しスラリー化した。次に、３５質量％過酸化水素水７８．７ｇと２６質量％のアンモニア水２６．５ｇを混合した水溶液を該含水酸化チタンスラリーに添加した。その後、２５℃を維持したまま３時間攪拌し、黄緑色で透明なチタン含有水溶液を得た。そこへ、クエン酸第１水和物２８．４ｇを添加した。その後、３０℃以下の温度で６時間保持した後、８０〜９５℃で１２時間保持することによりｐＨ６．２で透明なチタン含有水溶液１２０ｇを得た。得られたチタン含有水溶液を５８．５ｇ分取し、純水で希釈し８０ミリリットルとし、細孔容量０．８ミリリットル／ｇで四葉のアルミナ１００ｇに、常圧下で含浸（ポアフィリング法）した。その後、ロータリーエバポレータを用い減圧下、７０℃で１時間乾燥した後に、１２０℃で３時間乾燥し、最後に５００℃で４時間焼成し、ＴｉＯ2−５質量％担持アルミナ担体を得た。
[Preparation of hydrogenation catalyst]
A titanium-containing aqueous solution was prepared based on International Patent Publication WO2002 / 049963. Titanium oxides obtained by calcining for 4 hours at 500 ° C. The pure water of the hydrous titanium oxide powder 12.7g and 70g which is the ratio of (TiO 2) is 85 mass%, placed in a glass beaker having an inner volume of 1L, Stir to slurry. Next, an aqueous solution obtained by mixing 78.7 g of 35% by mass hydrogen peroxide and 26.5 g of 26% by mass ammonia water was added to the hydrous titanium oxide slurry. Then, it stirred for 3 hours, maintaining 25 degreeC, and obtained the yellow-green and transparent titanium containing aqueous solution. There, 28.4 g of citric acid monohydrate was added. Then, after hold | maintaining at the temperature of 30 degrees C or less for 6 hours, 120 g of transparent titanium containing aqueous solution by pH 6.2 was obtained by hold | maintaining at 80-95 degreeC for 12 hours. 58.5 g of the obtained titanium-containing aqueous solution was collected, diluted with pure water to 80 ml, and impregnated with 100 g of four-leaf alumina at a pore volume of 0.8 ml / g under normal pressure (pore filling method). Then, after drying for 1 hour at 70 ° C. under reduced pressure using a rotary evaporator, it was dried for 3 hours at 120 ° C. and finally calcined for 4 hours at 500 ° C. to obtain a TiO 2 -5 mass% supported alumina carrier.
次に、５００℃で４時間焼成することにより求めた、ニッケル酸化物（ＮｉＯ）の割合が５８．４質量％である塩基性炭酸ニッケル７５．３ｇ（ＮｉＯとして４４．０ｇ）、三酸化モリブデン２２０ｇ、正リン酸３４．５ｇ（Ｐ2Ｏ5として２９．３ｇ）に、純水を２５０ミリリットル加え、攪拌しながら８０℃で溶解し、室温にて冷却後、純水にて２６４ミリリットルに定容したニッケル・モリブデン含浸液を調製した。該含浸液を６０ミリリットル採取し、トリエチレングリコール６ｇを添加して、該ＴｉＯ2−５質量％担持アルミナ担体１００ｇの吸水量に見合うように、純水にて希釈・定容し、常圧にて含浸した。次いで、７０℃で１時間ロータリーエバポレータを用いて減圧下で乾燥した後、１２０℃で１６時間熱処理し、水素化触媒１を調製した。水素化触媒１の組成は、アルミナ５７質量％、ＴｉＯ2−３質量％、ＮｉＯ−６質量％、ＭｏＯ3−３質量％、Ｐ2Ｏ5−４質量％であった。 Next, 75.3 g of basic nickel carbonate (44.0 g as NiO) having a nickel oxide (NiO) ratio of 58.4% by mass obtained by firing at 500 ° C. for 4 hours, 220 g of molybdenum trioxide. Then, 250 ml of pure water was added to 34.5 g of orthophosphoric acid (29.3 g as P 2 O 5 ), dissolved at 80 ° C. with stirring, cooled at room temperature, and then fixed to 264 ml with pure water. A nickel-molybdenum impregnation solution was prepared. 60 milliliters of the impregnating solution was sampled, 6 g of triethylene glycol was added, diluted and constant volume with pure water to meet the water absorption of 100 g of the TiO 2 -5 mass% supported alumina carrier, Impregnated. Subsequently, after drying under reduced pressure using a rotary evaporator at 70 ° C. for 1 hour, heat treatment was performed at 120 ° C. for 16 hours to prepare a hydrogenation catalyst 1. The composition of the hydrogenation catalyst 1, the alumina 57 wt%, TiO 2 -3% by weight, NiO-6 mass%, MoO 3 -3 wt%, and the P 2 O 5 -4 wt%.
［水素化分解触媒の調製］
水素化分解触媒を、特許公報第２９０８９５９号を参照して、下記のようにニッケル・モリブデンを含む金属溶液を改質ゼオライト含有アルミナ担体に含浸担持して調製した。
Ｎａ2Ｏ含量が１．２質量％、ＳｉＯ2／Ａｌ2Ｏ3比（モル比）が５．０である粉末状のＮａＮＨ4Ｙ型ゼオライト２ｋｇをロータリーキルン内に投入し、７００℃で３時間セルフスチーミング処理を行い、スチーミングゼオライトを得た。このスチーミングゼオライト４００ｇに、濃度１．０モル／リットルの硝酸第二鉄水溶液４ｋｇと、該ゼオライト１ｋｇ当たりＨＮＯ3が１０モル量となる量の硝酸（濃度１．５モル／リットル）を添加し、攪拌下で７５℃にて２時間処理した。次いで、ろ過し、得られた固体分を温水にて数回洗浄し、所定の鉄含有酸処理ゼオライトをスラリー状態で回収し、改質ゼオライトを得た。改質ゼオライトのＳｉＯ2／Ａｌ2Ｏ3（モル比）は４０、格子定数は２．４３２ｎｍ、比表面積は７３６ｍ2／ｇ、Ｆｅ2Ｏ3の担持量は２．２質量％、Ｎａ2Ｏの含有量は０．１３質量％であった。酸量は０．４８ｍｍｏｌ／ｇであった。
なお、ゼオライトの酸量は、アンモニア昇温脱離法（ＮＨ3−ＴＰＤ）法で、以下のようにして測定した。
ゼオライトを測定セルに充填し、Ｈｅガスフローで４００℃、２時間処理して吸着水の除去を行った。１００℃で０．５％ＮＨ3／Ｈｅガスを６０分流して吸着を行った後、Ｈｅに室温の飽和水蒸気（２５Ｔｏｒｒ）を同伴させ、１００℃で４時間を流通させた。その後、Ｈｅを減圧下（１４０Ｔｏｒｒ）にて１００℃で６０分流通させた。次いで、１０〜７００℃まで２０℃／分で昇温して、脱離してくるＮＨ3の定量を質量検出計にて行った。
[Preparation of hydrocracking catalyst]
A hydrocracking catalyst was prepared by impregnating and supporting a modified zeolite-containing alumina support with a metal solution containing nickel and molybdenum as described below, with reference to Japanese Patent No. 2908959.
2 kg of powdered NaNH 4 Y-type zeolite having a Na 2 O content of 1.2% by mass and a SiO 2 / Al 2 O 3 ratio (molar ratio) of 5.0 was charged into a rotary kiln and kept at 700 ° C. for 3 hours. A self-steaming treatment was performed to obtain a steaming zeolite. To 400 g of this steaming zeolite, 4 kg of a ferric nitrate aqueous solution with a concentration of 1.0 mol / liter and nitric acid (concentration of 1.5 mol / liter) with an amount of 10 mol of HNO 3 per kg of the zeolite were added. For 2 hours at 75 ° C. with stirring. Next, filtration was performed, and the obtained solid content was washed several times with warm water, and a predetermined iron-containing acid-treated zeolite was recovered in a slurry state to obtain a modified zeolite. The modified zeolite has a SiO 2 / Al 2 O 3 (molar ratio) of 40, a lattice constant of 2.432 nm, a specific surface area of 736 m 2 / g, a supported amount of Fe 2 O 3 of 2.2% by mass, and Na 2 O. The content of was 0.13% by mass. The acid amount was 0.48 mmol / g.
The acid amount of zeolite was measured by the ammonia temperature programmed desorption method (NH 3 -TPD) method as follows.
Zeolite was filled in the measurement cell, and the adsorbed water was removed by treatment with He gas flow at 400 ° C. for 2 hours. Adsorption was performed by flowing 0.5% NH 3 / He gas at 100 ° C. for 60 minutes, and then he was allowed to flow with saturated water vapor (25 Torr) at room temperature for 4 hours at 100 ° C. Then, He was circulated for 60 minutes at 100 ° C. under reduced pressure (140 Torr). Next, the temperature was raised from 10 to 700 ° C. at 20 ° C./min, and the desorbed NH 3 was quantified with a mass detector.
また、硫酸アルミニウムの水溶液と、アンモニア水の水溶液を数回に分けて交互に添加することによって得たベーマイトゲルを、約９０℃にて約１２時間熟成することによって、アルミナスラリーを調製した。次に、該改質ゼオライトスラリー（水分量７０質量％）に、該アルミナスラリー（水分量８０質量％）を、該改質ゼオライトと該アルミナの割合が乾燥物基準の質量比でほぼ６５対３５となる割合で添加し、この混合スラリーを７０〜８０℃の温度に加熱しながら２時間ニーダーによって混合（捏和）した。こうして得た混合物の水分量を成型しやすい程度に調整した後、成型し、有効径１．５ｍｍの円柱状の成型物とし、これを約１１０℃で４時間乾燥し、さらに５５０℃にて３時間空気気流中で焼成し、所望のゼオライト含有組成物を得た。該ゼオライト含有組成物に、モリブデン酸アンモニウムと硝酸ニッケルの水溶液を用いてモリブデン成分とニッケル成分を含浸・担持した。この後、担持物を１１０℃の温度にて４時間乾燥し、さらに５５０℃にて３時間空気気流中で焼成し、所望の水素化分解触媒１を得た。水素化分解触媒１の組成は、該改質ゼオライト（鉄を含む）５６質量％、アルミナ３０質量％、ＮｉＯ−４質量％、ＭｏＯ3−１０質量％であった。水素化分解触媒１の細孔容積は０．４５ミリリットル／ｇであった。 Further, an alumina slurry was prepared by aging a boehmite gel obtained by alternately adding an aqueous solution of aluminum sulfate and an aqueous solution of ammonia in several portions at about 90 ° C. for about 12 hours. Next, the alumina slurry (water content: 80% by mass) is added to the modified zeolite slurry (water content: 70% by mass), and the ratio of the modified zeolite to the alumina is approximately 65:35 in terms of mass ratio based on dry matter. The mixture slurry was mixed (kneaded) by a kneader for 2 hours while heating to a temperature of 70 to 80 ° C. After adjusting the water content of the mixture thus obtained to a level that makes it easy to mold, it is molded into a cylindrical molded product having an effective diameter of 1.5 mm, dried at about 110 ° C. for 4 hours, and further at 550 ° C. for 3 hours. The desired zeolite-containing composition was obtained by firing in an air stream for a period of time. The zeolite-containing composition was impregnated and supported with a molybdenum component and a nickel component using an aqueous solution of ammonium molybdate and nickel nitrate. Thereafter, the supported product was dried at a temperature of 110 ° C. for 4 hours and further calcined in an air stream at 550 ° C. for 3 hours to obtain a desired hydrocracking catalyst 1. The composition of the hydrocracking catalyst 1, modified zeolite (containing iron) 56 wt% of alumina 30 wt%, NiO-4 wt%, and the MoO 3 -10 wt%. The pore volume of the hydrocracking catalyst 1 was 0.45 ml / g.
［ベンチ試験方法（水素化処理と水素化分解処理を行う）Ｉ］
高圧固定床流通式のベンチ反応器を２基直列に連結し、水素化分解反応を実施した。触媒は、前段（水素化反応器）に水素化触媒１を５０ミリリットル、後段（水素化分解反応器）に水素化分解触媒１を５０ミリリットル充填した。原料油は水素ガス（ボンベの純水素を昇圧して使用）とともに反応管の上段から導入するダウンフロー形式で流通させて反応評価を行った。前処理として、ＤＭＤＳ（ジメチルジスルフィド）を添加し硫黄濃度を２．０質量％に調整した、密度０．８４４ｇ／ｃｍ3の中東系軽油をベースとする予備硫化油を、水素ガスとともに流通させて温度２４０℃で４時間、２９０℃で９時間予備硫化を行なった。予備硫化後、硫黄分１．１質量％、密度０．８４６ｇ／ｃｍ3の中東系原油に切り替え、３１０℃で２４時間原料油硫化を行なった。次に、表２に記載した分解軽油に切り替えて、水素化分解実験を行なった。反応温度は前段、後段、各々の温度を３１０〜４１０℃の範囲で等温に制御した。反応圧力は水素化分解反応器出口で６．９ＭＰａ、水素／原料油比は水素化反応器入口で２，０００Ｎｍ3／キロリットル、ＬＨＳＶ（液空間速度）は水素化触媒１と水素化分解触媒１合計で０．６〜０．８ｈ-1の条件に調整し、ベンチ試験を行なった。実施例１〜３、比較例１，２の反応条件を表３に記す。
[Bench test method (perform hydrotreating and hydrocracking) I]
Two high pressure fixed bed flow type bench reactors were connected in series to carry out the hydrocracking reaction. As for the catalyst, 50 ml of the hydrogenation catalyst 1 was filled in the former stage (hydrogenation reactor), and 50 ml of the hydrogenolysis catalyst 1 was filled in the latter stage (hydrocracking reactor). The feedstock oil was circulated in a down-flow format introduced from the upper stage of the reaction tube together with hydrogen gas (uses pure hydrogen in a cylinder under pressure) to evaluate the reaction. As a pretreatment, a presulfurized oil based on a Middle East light oil with a density of 0.844 g / cm 3 and added with DMDS (dimethyl disulfide) and adjusted to a sulfur concentration of 2.0% by mass was circulated together with hydrogen gas. Presulfiding was performed at 240 ° C. for 4 hours and 290 ° C. for 9 hours. After preliminary sulfidation, the oil was switched to Middle Eastern crude oil having a sulfur content of 1.1 mass% and a density of 0.846 g / cm 3 , and raw material oil sulfidation was performed at 310 ° C. for 24 hours. Next, the hydrocracking experiment was conducted by switching to the cracked diesel oil described in Table 2. The reaction temperature was controlled to be isothermal within the range of 310 to 410 ° C. in the former stage and the latter stage. The reaction pressure is 6.9 MPa at the hydrocracking reactor outlet, the hydrogen / feed oil ratio is 2,000 Nm 3 / kiloliter at the hydrocracking reactor inlet, LHSV (liquid space velocity) is hydrogenation catalyst 1 and hydrocracking catalyst The bench test was conducted after adjusting the conditions to 0.6 to 0.8 h -1 in total. The reaction conditions of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 3.
［生成油の分析方法］
水素化触媒通過後の油については、硫化水素を除去するため、窒素ガスを流通し硫化水素ストリッピングを行なった。得られた試料の密度、動粘度（３０℃）を評価し、ＨＰＬＣ分析を行って各留分の容量（％）を求め、芳香族転化率、多環芳香族転化率を求めた。結果を表３に示す。
水素化分解触媒通過後のガスについては流量を測定するとともにガスクロにて分析し、生成油については秤量し、物質収支をとったところ、最低でも９６質量％以上の回収率が得られた。生成油については、２リットルないし４リットル回収し、１５段蒸留を行い、ＬＰＧ、軽質ガソリン（〜９０℃）、重質ガソリン（９０〜１９０℃）、軽油（１９０℃〜）に分留し、各々の質量を秤量した。軽質ガソリン、重質ガソリンについては、密度、硫黄分、窒素分、エングラー蒸留、ガソリン全組成分析、リサーチオクタン価の実測を行なった。結果を表３に示す。
[Analytical method of product oil]
The oil after passing through the hydrogenation catalyst was subjected to hydrogen sulfide stripping by circulating nitrogen gas in order to remove hydrogen sulfide. The density and kinematic viscosity (30 ° C.) of the obtained sample were evaluated, HPLC analysis was performed to determine the volume (%) of each fraction, and the aromatic conversion rate and polycyclic aromatic conversion rate were determined. The results are shown in Table 3.
As for the gas after passing through the hydrocracking catalyst, the flow rate was measured and analyzed by gas chromatography, and the product oil was weighed and the mass balance was taken. As a result, a recovery rate of 96% by mass or more was obtained. About 2 liters to 4 liters of the produced oil is recovered, subjected to 15-stage distillation, and fractionated into LPG, light gasoline (up to 90 ° C.), heavy gasoline (90 to 190 ° C.), and light oil (from 190 ° C.). Each mass was weighed. For light gasoline and heavy gasoline, density, sulfur content, nitrogen content, Engler distillation, gasoline total composition analysis, and research octane number were measured. The results are shown in Table 3.
実施例1、２
反応圧力を６．８６ＭＰａ、水素／油比を２，０００Ｎｍ3／ｋｌ、ＬＨＳＶを０．８ｈ-1として、表２に記載のＬＣＯ−１を通油してベンチ試験を行なった。水素化反応器の温度を３５０℃（実施例１）、３６０℃（実施例２）とし、水素化分解反応器の温度を４０５℃（実施例１）、４０１℃（実施例２）とした。ベンチ試験の実験条件と生成油の分析結果を表３に示す。
比較例１
水素化反応器の温度を３８０℃、水素化分解反応器の温度を３９６℃とした以外は実施例１、２と同様にベンチ試験を行なった。このときのベンチ試験の実験条件と生成油の分析結果を表３に示す。
Examples 1 and 2
A bench test was conducted by passing LCO-1 listed in Table 2 through a reaction pressure of 6.86 MPa, a hydrogen / oil ratio of 2,000 Nm 3 / kl, and an LHSV of 0.8 h −1 . The temperature of the hydrogenation reactor was 350 ° C. (Example 1) and 360 ° C. (Example 2), and the temperature of the hydrogenolysis reactor was 405 ° C. (Example 1) and 401 ° C. (Example 2). Table 3 shows the experimental conditions of the bench test and the analysis results of the produced oil.
Comparative Example 1
Bench tests were conducted in the same manner as in Examples 1 and 2 except that the temperature of the hydrogenation reactor was 380 ° C and the temperature of the hydrocracking reactor was 396 ° C. Table 3 shows the experimental conditions of the bench test and the analysis results of the produced oil.
実施例１，２と比較例１の考察
水素化反応器における多環芳香族転化率は、実施例１で７６．８％、実施例２で７４．４％、比較例１で６８．４％であった。一方、芳香族転化率は、実施例１で０．４％、実施例２で１．２％、比較例１で３．５％であった。得られた重質ガソリン基材の得率（原料油基準）と蒸留性状は実施例１、実施例２と比較例１とで同じであるが、比較例１は、重質ガソリンのＲＯＮ、重質ガソリンに含まれる一環芳香族（Ｃ７〜Ｃ９）とＣ８芳香族の収率が実施例１、実施例２より少ないことがわかる。これは水素化反応器における多環芳香族転化率が６８．４％と低いにもかかわらず、芳香族転化率が３．５％と高すぎることに起因している。すなわち、水素化反応器において、多環芳香族炭化水素の一環芳香族炭化水素への転換は不十分でありながら、一環芳香族を過剰に水素化し、ナフテン炭化水素に添加したため、と考えられる。なお、軽質ガソリンのＲＯＮは実施例１、２の方が比較例１より高い。これは実施例の方が比較例よりもベンゼンの濃度が高く、シクロヘキサンやメチルシクロペンタンのようなナフテン炭化水素の濃度が低いためであり、重質ガソリンと同様の傾向を示した。よって、重質ガソリン基材中の有用成分である一環芳香族成分、特にＣ８芳香族成分を高収率で得るには、水素化反応器における多環芳香族転化率ならびに芳香族転化率を本発明の範囲に制御することの重要性がここに示された。
Consideration of Examples 1 and 2 and Comparative Example 1 The polycyclic aromatic conversion in the hydrogenation reactor was 76.8% in Example 1, 74.4% in Example 2, and 68.4% in Comparative Example 1. Met. On the other hand, the aromatic conversion was 0.4% in Example 1, 1.2% in Example 2, and 3.5% in Comparative Example 1. The yield (based on feedstock) and the distillation properties of the obtained heavy gasoline base material are the same in Example 1, Example 2 and Comparative Example 1, but Comparative Example 1 shows the RON and heavy weight of heavy gasoline. It can be seen that the yields of monocyclic aromatics (C7 to C9) and C8 aromatics contained in the quality gasoline are lower than those in Examples 1 and 2. This is due to the fact that the aromatic conversion is too high at 3.5% in spite of the low polycyclic aromatic conversion at 68.4% in the hydrogenation reactor. That is, it is considered that in the hydrogenation reactor, conversion of polycyclic aromatic hydrocarbons to partial aromatic hydrocarbons was insufficient, but partial aromatics were excessively hydrogenated and added to naphthene hydrocarbons. The RON of light gasoline is higher in Examples 1 and 2 than in Comparative Example 1. This is because the concentration of benzene was higher in the examples than in the comparative example, and the concentration of naphthene hydrocarbons such as cyclohexane and methylcyclopentane was lower, indicating a tendency similar to that of heavy gasoline. Therefore, in order to obtain a single aromatic component, particularly a C8 aromatic component, which is a useful component in a heavy gasoline base material, in a high yield, the polycyclic aromatic conversion rate and aromatic conversion rate in the hydrogenation reactor are set as follows. The importance of controlling within the scope of the invention has been demonstrated here.
実施例３、比較例２
反応圧力を６．８６ＭＰａ、水素／油比を２，０００Ｎｍ3／ｋｌ、ＬＨＳＶを０．８ｈ-1として、表１記載のＬＣＯ−２を通油してベンチ試験を行なった。実施例３では水素化反応器の温度を３１０℃、水素化分解反応器の温度を３９３℃に設定した。比較例１では水素化反応器の温度を３３０℃、水素化分解反応器の温度を３９０℃に設定した。ベンチ試験の実験条件と生成油の分析結果を表３に示す。
Example 3 and Comparative Example 2
A bench test was conducted by passing LCO-2 listed in Table 1 through a reaction pressure of 6.86 MPa, a hydrogen / oil ratio of 2,000 Nm 3 / kl, and an LHSV of 0.8 h −1 . In Example 3, the temperature of the hydrogenation reactor was set to 310 ° C, and the temperature of the hydrocracking reactor was set to 393 ° C. In Comparative Example 1, the temperature of the hydrogenation reactor was set to 330 ° C., and the temperature of the hydrocracking reactor was set to 390 ° C. Table 3 shows the experimental conditions of the bench test and the analysis results of the produced oil.
実施例３と比較例２の考察
芳香族転化率が２．７％と高い場合（比較例２）よりも、芳香族転化率が−０．４％と低い場合（実施例３）の方が重質ガソリン基材のオクタン価、重質ガソリン基材に含まれる一環芳香族とＣ８芳香族の収率が高いことがわかる。軽質ガソリンのＲＯＮは実施例３の方が比較例２より高い。これは、実施例の方が比較例よりもベンゼンの濃度が高く、シクロヘキサンやメチルシクロペンタンのようなナフテン炭化水素の濃度が低いためであり、重質ガソリンと同様の傾向を示した。このように、原料油の高芳香族含有炭化水素油の種類が変っても、芳香族転化率を本発明の範囲に制御することの重要性がここに示された。
尚、実施例３で、芳香族転化率（容量％）が負の値を示し、芳香族分が微増したように見えるのは、水素化工程で部分的に（不完全に）水素化された芳香族化合物の容積が、元の芳香族化合物の容積と比較して増大したことによると考えられる。
Consideration of Example 3 and Comparative Example 2 When the aromatic conversion is as low as −0.4% (Example 3) than when the aromatic conversion is as high as 2.7% (Comparative Example 2). It can be seen that the octane number of the heavy gasoline base material and the yield of the partial aromatic and C8 aromatic contained in the heavy gasoline base material are high. The RON of light gasoline is higher in Example 3 than in Comparative Example 2. This is because the concentration of benzene was higher in the example than in the comparative example, and the concentration of naphthene hydrocarbons such as cyclohexane and methylcyclopentane was lower, indicating a tendency similar to that of heavy gasoline. Thus, the importance of controlling the aromatic conversion rate within the scope of the present invention is shown here even if the type of the highly aromatic hydrocarbon oil of the feedstock is changed.
In Example 3, the aromatic conversion (volume%) showed a negative value, and the aromatic content seemed to slightly increase because it was partially (incompletely) hydrogenated in the hydrogenation step. This is probably because the volume of the aromatic compound increased compared to the volume of the original aromatic compound.
［ベンチ試験方法（水素化処理と水素化分解処理を行う）II］
前記ベンチ試験方法（Ｉ）で用いた高圧固定床流通式のベンチ反応器を２基連結せずに設置し、前段（水素化反応器）の出口油を回収し、その性状を確認した後に、後段（水素化分解反応器）に導入し、水素化分解反応を実施した。
用いた触媒及びその充填量、予備硫化方法は、ベンチ試験方法（Ｉ）と同様の方法で行った。また、反応条件は、実施例４では、芳香族転化率が１．０質量％、比較例３では、芳香族転化率が７．３質量％になるように設定して調整し、ベンチ試験を行った。実施例４、比較例３の反応条件を表４に示す。
[Bench test method (perform hydrotreating and hydrocracking) II]
After installing the high pressure fixed bed flow type bench reactor used in the bench test method (I) without connecting two reactors, collecting the outlet oil of the previous stage (hydrogenation reactor), and confirming its properties, It introduce | transduced into the back | latter stage (hydrocracking reactor), and hydrocracking reaction was implemented.
The catalyst used, its filling amount, and the presulfiding method were the same as the bench test method (I). The reaction conditions were adjusted and adjusted so that the aromatic conversion rate was 1.0 mass% in Example 4 and the aromatic conversion rate was 7.3 mass% in Comparative Example 3, and the bench test was performed. went. The reaction conditions of Example 4 and Comparative Example 3 are shown in Table 4.
実施例４
水素化反応器の反応圧力を６．８６ＭＰａ、反応温度を３４８℃、水素／油比を１，７００Ｎｍ3／ｋｌ、ＬＨＳＶを１．６ｈ-1として、表２に記載のＬＣＯ−１を通油してベンチ試験を行なった。水素化分解反応器の反応圧力を６．８６ＭＰａ、反応温度を３８２℃、水素／油比を２，０００Ｎｍ3／ｋｌ、ＬＨＳＶを１．０ｈ-1とした。ベンチ試験の実験条件と生成油の分析結果を表４に示す。
比較例３
水素化反応器の反応圧力を７．８４ＭＰａ、反応温度を３４０℃、水素／油比を１，３００Ｎｍ3／ｋｌ、ＬＨＳＶを２．０ｈ-1とし、水素化分解反応器の温度を３６８℃とした以外は実施例４と同様にベンチ試験を行なった。このときのベンチ試験の実験条件と生成油の分析結果を表４に示す。
Example 4
Through the LCO-1 listed in Table 2, the reaction pressure of the hydrogenation reactor was 6.86 MPa, the reaction temperature was 348 ° C., the hydrogen / oil ratio was 1,700 Nm 3 / kl, and the LHSV was 1.6 h −1. Then, a bench test was conducted. The reaction pressure of the hydrocracking reactor was 6.86 MPa, the reaction temperature was 382 ° C., the hydrogen / oil ratio was 2,000 Nm 3 / kl, and the LHSV was 1.0 h −1 . Table 4 shows the experimental conditions of the bench test and the analysis results of the produced oil.
Comparative Example 3
The reaction pressure of the hydrogenation reactor is 7.84 MPa, the reaction temperature is 340 ° C., the hydrogen / oil ratio is 1,300 Nm 3 / kl, the LHSV is 2.0 h −1, and the temperature of the hydrocracking reactor is 368 ° C. A bench test was conducted in the same manner as in Example 4 except that. Table 4 shows the experimental conditions of the bench test and the analysis results of the produced oil.
実施例４と比較例３の考察
芳香族転化率が７．３％と高い場合（比較例４）よりも、芳香族転化率が１．０％と低い場合（実施例４）の方が重質ガソリン基材のオクタン価、重質ガソリン基材に含まれるＣ８芳香族、及びＣ７、Ｃ９芳香族の収率が高いことがわかる。このように、水素化反応器の設置方法が変っても、芳香族転化率を本発明の範囲に制御することの重要性がここに示された。
Consideration of Example 4 and Comparative Example 3 When the aromatic conversion rate is as low as 1.0% (Example 4) than when the aromatic conversion rate is as high as 7.3% (Comparative Example 4). It can be seen that the octane number of the high quality gasoline base, the C8 aromatics contained in the heavy gasoline base, and the yields of C7 and C9 aromatics are high. Thus, the importance of controlling the aromatic conversion rate within the scope of the present invention is shown here even if the installation method of the hydrogenation reactor is changed.
本発明によれば、接触分解軽油（ＬＣＯ）などの高芳香族炭化水素油を原料とし、一環芳香族炭化水素、特に炭素数８の芳香族炭化水素の収率が高い、高オクタン価ガソリン留分を効率的に製造できる。
また、本発明によれば、圧力・温度が比較的温和な条件で高オクタン価のガソリン留分を製造できるため、省資源・省エネルギーに資する製造方法を提供することができる。
また、本発明によれば、高オクタン価を付与する留分であるとともに、基礎化学原料として有用な炭素数６〜８の芳香族化合物を多く含む留分を提供することができる。したがって、広く産業界において有用な技術として利用できる。
According to the present invention, a high-octane gasoline fraction that uses high aromatic hydrocarbon oil such as catalytic cracking light oil (LCO) as a raw material and has a high yield of partially aromatic hydrocarbons, particularly aromatic hydrocarbons having 8 carbon atoms. Can be manufactured efficiently.
In addition, according to the present invention, since a high-octane gasoline fraction can be produced under relatively mild pressure and temperature, a production method that contributes to resource saving and energy saving can be provided.
Moreover, according to this invention, while being a fraction which provides a high octane number, the fraction which contains many C6-C8 aromatic compounds useful as a basic chemical raw material can be provided. Therefore, it can be widely used as a technique useful in the industry.
Claims (3)
多環芳香族転化率（％）＝（ａ／ｂ）×１００（％） ・・・（１）
（式中、ａは、水素化工程における多環芳香族濃度の減少幅，ｂは原料中の多環芳香族濃度を示す。）
芳香族転化率（％）＝（Ａ／Ｂ）×１００（％） ・・・（２）
（式中、Ａは、水素化工程における芳香族濃度の減少幅，Ｂは原料中の芳香族濃度を示す。） The first step of hydrotreating from a highly aromatic hydrocarbon oil, the second step of hydrocracking the product oil obtained in the first step, and the cracked product oil obtained in the second step A method for producing a gasoline fraction having a third step of distillation, wherein the polycyclic aromatic conversion calculated by the following formula (1) by the hydrotreating step is 70% or more, and the following formula ( A method for producing a gasoline base material using a highly aromatic hydrocarbon oil as a raw material, wherein the hydrotreating conditions are adjusted so that the aromatic conversion calculated in 2) is 2.0% or less.
Polycyclic aromatic conversion (%) = (a / b) × 100 (%) (1)
(In the formula, “a” represents a decrease in the polycyclic aromatic concentration in the hydrogenation step, and “b” represents the polycyclic aromatic concentration in the raw material.)
Aromatic conversion rate (%) = (A / B) × 100 (%) (2)
(In the formula, A represents the reduction range of the aromatic concentration in the hydrogenation step, and B represents the aromatic concentration in the raw material.)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011116872A (en) * | 2009-12-04 | 2011-06-16 | Jx Nippon Oil & Energy Corp | Method for producing monocyclic aromatic hydrocarbon |
| JP2012207171A (en) * | 2011-03-30 | 2012-10-25 | Jx Nippon Oil & Energy Corp | Method of producing gasoline base material |
| CN103666553A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Method of hydro-conversion of polycyclic aromatic hydrocarbons |
| JP2014196395A (en) * | 2013-03-29 | 2014-10-16 | Ｊｘ日鉱日石エネルギー株式会社 | Method for manufacturing petroleum product |
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| JP2007154151A (en) * | 2005-11-11 | 2007-06-21 | Toray Ind Inc | Method for producing 6-8c aromatic hydrocarbon |
| JP2008297452A (en) * | 2007-05-31 | 2008-12-11 | Japan Energy Corp | Method for producing alkylbenzene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007154151A (en) * | 2005-11-11 | 2007-06-21 | Toray Ind Inc | Method for producing 6-8c aromatic hydrocarbon |
| JP2008297452A (en) * | 2007-05-31 | 2008-12-11 | Japan Energy Corp | Method for producing alkylbenzene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011116872A (en) * | 2009-12-04 | 2011-06-16 | Jx Nippon Oil & Energy Corp | Method for producing monocyclic aromatic hydrocarbon |
| JP2012207171A (en) * | 2011-03-30 | 2012-10-25 | Jx Nippon Oil & Energy Corp | Method of producing gasoline base material |
| CN103666553A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Method of hydro-conversion of polycyclic aromatic hydrocarbons |
| JP2014196395A (en) * | 2013-03-29 | 2014-10-16 | Ｊｘ日鉱日石エネルギー株式会社 | Method for manufacturing petroleum product |
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