JPH02247293A - Production of high boiling point, high aromatic solvent - Google Patents
Production of high boiling point, high aromatic solventInfo
- Publication number
- JPH02247293A JPH02247293A JP6608289A JP6608289A JPH02247293A JP H02247293 A JPH02247293 A JP H02247293A JP 6608289 A JP6608289 A JP 6608289A JP 6608289 A JP6608289 A JP 6608289A JP H02247293 A JPH02247293 A JP H02247293A
- Authority
- JP
- Japan
- Prior art keywords
- fraction
- boiling point
- reformed
- reforming step
- reforming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000009835 boiling Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003849 aromatic solvent Substances 0.000 title claims description 9
- 239000003350 kerosene Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 239000012188 paraffin wax Substances 0.000 claims abstract description 9
- 238000002407 reforming Methods 0.000 claims description 30
- 238000007700 distillative separation Methods 0.000 claims 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000006057 reforming reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000011820 acidic refractory Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- -1 monocyclic aromatic compound Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、灯油留分或いは灯油留分からノルマルパラフ
ィンを回収した後のラフィネートを用いて、高沸点、高
芳香族溶剤を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a high boiling point, highly aromatic solvent using a kerosene fraction or a raffinate after recovering normal paraffins from a kerosene fraction.
［従来の技術］
沸点範囲が１８５〜２２０℃、或いは２０５〜２４５℃
、さらにはこの両範囲を含み、主として芳香族成分から
なる留分は、フェノール樹脂、アルキッド樹脂、ユリア
樹脂、メラミン樹脂、アクリル樹脂等を用いた焼付は塗
料用の溶剤及びシンナー、金属部品の洗浄溶剤、農薬用
の乳剤、機械用の油剤配合剤さらには反応系の溶剤とし
て使用されている。これらの溶剤は、溶解性の観点から
混合アニリン点が、１８５〜２２０℃の沸点範囲のもの
は２１℃以下、２０５〜２４５℃のものは１８℃以下で
あることが要求されている。[Prior art] Boiling point range is 185-220°C or 205-245°C
Furthermore, the fraction containing both of these ranges and mainly consisting of aromatic components is used as a solvent and thinner for paints, and for cleaning metal parts, for baking using phenolic resins, alkyd resins, urea resins, melamine resins, acrylic resins, etc. It is used as a solvent, an emulsion for agricultural chemicals, an oil compounding agent for machinery, and a solvent for reaction systems. From the viewpoint of solubility, these solvents are required to have a mixed aniline point of 21°C or less for those with a boiling point of 185-220°C, and 18°C or less for those with a boiling point of 205-245°C.
従来、この種の溶剤は、石炭タール油から回収する方法
、エチレンクラッカ・−ボトムと０９ヘビヤー（ナフサ
の改質反応により得られた改質油中から回収された炭素
数９以上の留分）を混合して水素化処理する方法、ナフ
タレンのアルキル化、単環芳香族化合物の二核体化等に
より製造されている。これらの方法は、一般に製造コス
トが高いという問題があった。Conventionally, this type of solvent has been recovered from coal tar oil, using ethylene cracker bottoms and 09 heavier (a fraction with a carbon number of 9 or more recovered from reformed oil obtained by a naphtha reforming reaction). It is produced by mixing and hydrogenating, alkylating naphthalene, converting a monocyclic aromatic compound into a dinuclear compound, etc. These methods generally have the problem of high manufacturing costs.
ところで、灯油留分を接触改質することにより高沸点、
高芳香族成分を含有する留分が生成することが報告され
ている〔石油学会、Ｊ、Ｖｏｌ、１３゜Ｎｏ、６（１９
７０）、Ｐ４６８〜４７４） 、しかし、灯油留分の改
質反応において、２１℃以下の混合アニリン点を有する
１８５〜２２０℃の留分や１８℃以下の混合アニリン点
を有する２０５〜２４５℃の留分を得るためには、過酷
な反応条件としなければならず、このため触媒寿命が極
めて短くなり、工業生産上問題が有ることが判明した。By the way, by catalytically reforming kerosene fraction, high boiling point,
It has been reported that a fraction containing highly aromatic components is produced [Petroleum Institute of Japan, J, Vol, 13° No. 6 (19
70), P468-474) However, in the reforming reaction of kerosene fractions, the 185-220°C fraction with a mixed aniline point of 21°C or lower and the 205-245°C fraction with a mixed aniline point of 18°C or lower are used. In order to obtain a fraction, harsh reaction conditions are required, which leads to an extremely short catalyst life, which has been found to be a problem in industrial production.
［発明が解決しようとする課題］
本発明は、上述のような問題点を解決するもので、本発
明の目的は、安い製造コストで、２１℃以下や１８℃以
下の混合アニリン点を有する溶解性に優れ九高沸点、高
芳香族含有溶剤を製造する方法を提供することにある。[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems, and an object of the present invention is to produce a melting aniline having a mixed aniline point of 21°C or lower or 18°C or lower at a low manufacturing cost. The object of the present invention is to provide a method for producing a solvent with excellent properties, a high boiling point, and a high aromatic content.
［課題を解決するための手段］
本発明は、灯油留分または灯油留分からノルマルパラフ
ィンを回収した後のラフィネートを第１の改質工程で改
質し、次いで得られた生成油から２２０℃以下もしくは
２４５℃以下の留分を蒸留分離し、当該留分を第２の改
質工程で改質した後、１．８５〜２２０℃及び２０５〜
２４５℃の範囲の留分を蒸留分離することからなるもの
である。[Means for Solving the Problems] The present invention involves reforming a kerosene fraction or a raffinate after normal paraffin is recovered from a kerosene fraction in a first reforming step, and then converting the resulting product oil to 220°C or lower. Alternatively, after distilling and separating the fraction at 245°C or lower and modifying the fraction in the second reforming step,
It consists of distilling and separating a fraction in the range of 245°C.
本発明にいう灯油留分とは、蒸留分離操作により１５０
〜３００℃の温度範囲で留出する留分をいい、原油を常
圧蒸留して得られた直留の灯油留分の他、石油の各留分
、残渣等の熱分解、接触分解、水素化分解、アルキレー
ション、その他の精製処理等により得られた前記沸点範
囲の留分等も用いることができることはいうまでもない
。この灯油留分は、好ましくは、硫黄分及び窒素台が、
５０ｐｐｍ以下としたものが良く、これは、一般に採用
されている水添脱硫処理方法で、通常の脱硫条件、例え
ば、アルミナあるいはシリカ−アルミナ等の担体に、コ
バルト、ニッケル、モリブデン、タングステン等の１種
以上を担持した触媒を用い、２５０〜４３０℃の温度、
１０〜２００ｋｇ／ｄの圧力、液空間速度（ＬＨＳ Ｖ
）０． ｉ 〜１５ ｈ−’、水素循環量５０〜１４０
ＯＮｎ（／ｋｆ＋の条件下で脱硫した脱硫前を用いるこ
とが好ましい。The kerosene fraction referred to in the present invention means 150% by distillation separation operation.
Refers to fractions distilled in the temperature range of ~300℃, including straight-run kerosene fraction obtained by atmospheric distillation of crude oil, as well as various petroleum fractions, thermal cracking of residues, catalytic cracking, hydrogen It goes without saying that fractions having the above-mentioned boiling point range obtained by chemical decomposition, alkylation, other purification treatments, etc. can also be used. This kerosene fraction preferably has a sulfur content and a nitrogen content of
It is best to set the concentration to 50 ppm or less, and this is a commonly used hydrodesulfurization treatment method under normal desulfurization conditions, such as cobalt, nickel, molybdenum, tungsten, etc. Using a catalyst supporting more than one species, at a temperature of 250 to 430°C,
Pressure from 10 to 200 kg/d, liquid hourly space velocity (LHS V
)0. i ~15 h-', hydrogen circulation amount 50 ~ 140
It is preferable to use the undesulfurized product desulfurized under the condition of ONn(/kf+).
尚、本発明においては、上記灯油留分の他、この灯油留
分からノルマルパラフィンを回収したラフィネートを用
いても良く、この場合部、改質反応条件をマイルドにす
ることができる。In the present invention, in addition to the above-mentioned kerosene fraction, a raffinate obtained by recovering normal paraffin from this kerosene fraction may be used, and in this case, the reforming reaction conditions can be made milder.
このノルマルパラフィンの除去は、このノルマルパラフ
ィンの除去は、ゼオライトを用いた吸着分離方法や尿素
アダクトによる分離方法を用いて行なうことができる。Removal of this normal paraffin can be carried out using an adsorption separation method using zeolite or a separation method using a urea adduct.
このラフィネートは、ノルマルパラフィンを５０〜９５
％程度の回収率で回収除去したもので充分である。This raffinate contains 50 to 95% normal paraffin.
% recovery rate is sufficient.
本発明の第１及び第２の改質工程は、一般にナフサ留分
等から高オクタン価ガソリンを製造する方法として広く
用いられている接触改質法を採用することができる。本
発明においては、第１と第２の改質工程とは、同じ装置
、条件で反応させても、異なる装置、条件で反応させて
も良い。この改質反応は、例えば、アルミナを担体とし
て白金、または白金に加えてレニウム、ゲルマニウム、
すず、イリジウム、ルテニウム等を担持した触媒を用い
、４００〜５５０℃の温度、１〜５０ｋｇ／ｃ＋ｄの圧
力、液空間速度（ＬＨ３Ｖ）０．１〜３ｈ″□′、水素
／油モル比０．５〜２０の条件下に行うことができる。The first and second reforming steps of the present invention can employ a catalytic reforming method that is widely used as a method for producing high octane gasoline from naphtha fraction and the like. In the present invention, the first and second reforming steps may be performed using the same equipment and conditions, or may be performed using different equipment and conditions. This modification reaction can be carried out using, for example, platinum using alumina as a carrier, or rhenium, germanium, etc. in addition to platinum.
A catalyst supporting tin, iridium, ruthenium, etc. is used at a temperature of 400 to 550°C, a pressure of 1 to 50 kg/c+d, a liquid hourly space velocity (LH3V) of 0.1 to 3 h''□', and a hydrogen/oil molar ratio of 0. It can be carried out under 5 to 20 conditions.
また、他の改質反応の方法としては、ゼオライト若しく
は結晶性アルミノシリケート、シリカ、アルミナ、ジル
コニア、チタニア、クロミア、固体リン酸、またはイン
ジウム、ランタン、マンガン、セリウム若しくはスズ等
の酸化物、或いは、これらの２種以上の混合物を含む酸
性耐火物、またはこれらに、白金、パラジウム、レニウ
ム等の金属類を含有させるがあるいは担持させた触媒等
を用いて、２５０〜７００℃の温度、ｌ 〜１００ｋｇ
／ｃｏ？（７）圧力、ｏ、１〜２ｏｈ−１のＬＨ３Ｖ、
水素／油モル比０．５〜２０（７）条件下に行なわせる
こともできる。In addition, other modification reaction methods include zeolite or crystalline aluminosilicate, silica, alumina, zirconia, titania, chromia, solid phosphoric acid, or oxides such as indium, lanthanum, manganese, cerium, or tin, or Using an acidic refractory containing a mixture of two or more of these, or a catalyst containing or supporting metals such as platinum, palladium, and rhenium, at a temperature of 250 to 700°C, 1 to 100 kg
/co? (7) Pressure, o, LH3V of 1 to 2 oh-1,
It can also be carried out under conditions where the hydrogen/oil molar ratio is 0.5 to 20 (7).
この改質反応はりアクタ一部が固定床の反応装置を用い
てもよいが、触媒連続再生法を付加した移動床からなる
反応装置を用いることが、効率上好ましい。Although a reactor in which part of the reforming reaction actor is a fixed bed may be used, it is preferable in terms of efficiency to use a reactor comprising a moving bed to which a continuous catalyst regeneration method is added.
本発明では、第１の改質工程で得られた生成油を、蒸留
分離した後、再度筒２の改質工程へ供給して改質させる
。これは、ワンスルーの改質で芳香族溶剤としての要求
される溶解性の指標である混合アニリン点を充分に低く
することは、工業的に極めて困難であることが判明した
ためである。第２の改質工程へ供給する留分は、１８５
〜２２０℃の範囲の留分の溶剤を得るためには２２０℃
以下の留分、特には分解軽質留分を除去した１５０〜２
２０℃の沸点範囲を主として含む留分を用いると、収量
を高めることができ、好ましい。また、２０５〜２４５
℃の範囲の留分の溶剤を得るためには２４５℃以下の留
分、特には分解軽質留分等を除去した、１８０〜２４５
℃、さらには２０５〜２４５℃の沸点範囲を主として含
む留分を用いることが上記と同様の理由から好ましい。In the present invention, the produced oil obtained in the first reforming step is separated by distillation and then supplied to the reforming step in cylinder 2 again to be reformed. This is because it has been found that it is industrially extremely difficult to sufficiently lower the mixed aniline point, which is an index of solubility required as an aromatic solvent, through one-through modification. The fraction supplied to the second reforming step is 185
220°C to obtain solvent for fractions in the range ~220°C.
150-2 after removing the following fractions, especially cracked light fractions:
It is preferable to use a fraction mainly having a boiling point range of 20° C. since the yield can be increased. Also, 205-245
In order to obtain a solvent for fractions in the range of 180 to 245 °C, fractions below 245 °C, especially decomposed light fractions, etc., are removed.
For the same reason as above, it is preferable to use a fraction mainly having a boiling point range of 205 to 245°C.
尚、この第２の工程へは、１８５〜２２０℃の沸点範囲
の溶剤と２０５〜２４５℃の沸点範囲の溶剤となる第１
の改質油の留分とは分離することなく、すなわち、例え
ば、１５０〜２４５℃の留分を供給して、改質し、その
後に、上記沸点範囲にそれぞれ分離することでも良いこ
とは云うまでもない。In addition, to this second step, a solvent with a boiling point range of 185 to 220°C and a first solvent with a boiling point range of 205 to 245°C are added.
It should be noted that it is also possible to supply the fraction of 150 to 245°C without separating it from the reformed oil fraction, reform it, and then separate it into the above boiling point range. Not even.
以上のようにして得られる生成油から１８５〜２２０℃
の範囲の留分を蒸留して、回収することにより高沸点、
高芳香族含有量の溶剤を製品として得ることができる。185-220℃ from the product oil obtained as above.
By distilling and recovering fractions in the range of
Solvents with high aromatic content can be obtained as products.
［実施例］
（実施例１〜８）
灯油留分を水添脱硫した第１表として示した性状を有す
る脱硫灯油留分及びこの灯油留分からゼオライトを用い
て、ノルマルパラフィンを９０重量％回収した第１表に
示した性状を有するラフィネートを原料とし、第１の改
質工程として、白金を０．２重量％担持したアルミナ担
体の接触改質触媒を用いて、４８０℃、圧力２５ｋｇ／
ｌｎＧ、ＬＨ３Ｖ０，８ｈ−’、水素／油モル比６の条
件下で改質反応を行った。この生成油から、第２表に記
載した留分に蒸留分離したものを、前記の改質触媒を用
い、４８０℃、圧力２５ｋｇ／ ｃＩｄＧ、 Ｌ ）（
、、Ｓ Ｖ ０ 、８ ｈ−’、水素／油モル比６の条
件の第２の改質工程で改質し、得られた生成油から１８
５〜２２０℃の留分または２０５〜２４５℃の留分を得
た。この性状を第２表に示した。[Example] (Examples 1 to 8) Using a desulfurized kerosene fraction having the properties shown in Table 1 obtained by hydrodesulfurizing a kerosene fraction and zeolite from this kerosene fraction, 90% by weight of normal paraffin was recovered. Raffinate having the properties shown in Table 1 was used as a raw material, and in the first reforming step, a catalytic reforming catalyst of an alumina carrier supporting 0.2% by weight of platinum was used at 480°C and a pressure of 25kg/
The reforming reaction was carried out under the conditions of lnG, LH3V0,8h-', and a hydrogen/oil molar ratio of 6. The resulting oil was distilled and separated into the fractions listed in Table 2, using the above-mentioned reforming catalyst at 480°C and a pressure of 25 kg/cIdG, L) (
,, S V 0 , 8 h-', 18
A fraction between 5 and 220°C or a fraction between 205 and 245°C was obtained. The properties are shown in Table 2.
（比較例１〜２）
上記実施例で用いた脱硫灯油留分及びラフィネートを用
い、実施例の第１の改質工程として用いた触媒を用い、
４８０℃、圧力２５ｋｇ／ｃｎｆＧ、ＬＨ３Ｖ０．４ｈ
−’、水素／油モル比６の条件下で改質反応を行った。(Comparative Examples 1 to 2) Using the desulfurized kerosene fraction and raffinate used in the above examples, and using the catalyst used in the first reforming step of the examples,
480℃, pressure 25kg/cnfG, LH3V0.4h
-', the reforming reaction was carried out under the conditions of a hydrogen/oil molar ratio of 6.
この改質油を蒸留分離し、１９５〜２１５℃の留分及び
２１５〜２３５℃の留分を得た。この性状を第３表に示
した。This reformed oil was separated by distillation to obtain a 195-215°C fraction and a 215-235°C fraction. The properties are shown in Table 3.
（以下余白）
これらの結果から、改質油の所定の留分について２段階
の改質反応させると、１段の場合のＬ ＨＳ Ｖを考慮
したとして、も、これに比較して、混合アニリン点の低
い溶剤が得られることがわかる。(Left below) From these results, it can be seen that when a predetermined fraction of reformed oil is subjected to a two-stage reforming reaction, the mixed aniline It can be seen that a solvent with a low point can be obtained.
［発明の効果］
本発明は、灯油留分を一度改質反応し、その改質油を蒸
留分離して、所定の留分のみを再度改質反応させるよう
にしたため、安い製造コストで、混合アニリン点が２１
℃以下さらには１８℃以下という溶解性に優れた高沸点
、高芳香族含有溶剤を製造できるという格別の効果を有
する。[Effects of the Invention] The present invention allows kerosene fractions to be reformed once, the reformed oil to be separated by distillation, and only a predetermined fraction to be reformed again. Aniline point is 21
It has a special effect of being able to produce a high boiling point, high aromatic content solvent with excellent solubility of 18°C or lower.
Claims (6)
れた生成油から２２０℃以下の留分を蒸留分離し、当該
留分を第２の改質工程で改質した後、１８５〜２２０℃
の範囲の留分を蒸留分離することを特徴とする高沸点、
高芳香族溶剤の製造方法。(1) The kerosene fraction was reformed in the first reforming step, then the fraction below 220°C was separated by distillation from the resulting product oil, and the fraction was reformed in the second reforming step. After that, 185-220℃
high boiling point, characterized by distillative separation of fractions in the range of
A method for producing a highly aromatic solvent.
れた生成油から２４５℃以下の留分を蒸留分離し、当該
留分を第２の改質工程で改質した後、１８５〜２２０℃
の範囲の留分を蒸留分離することを特徴とする高沸点、
高芳香族溶剤の製造方法。(2) The kerosene fraction was reformed in the first reforming step, then the fraction below 245°C was separated by distillation from the resulting product oil, and the fraction was reformed in the second reforming step. After that, 185-220℃
high boiling point, characterized by distillative separation of fractions in the range of
A method for producing a highly aromatic solvent.
れた生成油から２４５℃以下の留分を蒸留分離し、当該
留分を第２の改質工程で改質した後、２０５〜２４５℃
の範囲の留分を蒸留分離することを特徴とする高沸点、
高芳香族溶剤の製造方法。(3) The kerosene fraction was reformed in the first reforming step, then the fraction below 245°C was separated by distillation from the resulting product oil, and the fraction was reformed in the second reforming step. After, 205-245℃
high boiling point, characterized by distillative separation of fractions in the range of
A method for producing a highly aromatic solvent.
ラフィネートを第１の改質工程で改質し、次いで得られ
た生成油から２２０℃以下の留分を蒸留分離し、当該留
分を第２の改質工程で改質した後、１８５〜２２０℃の
範囲の留分を蒸留分離するすることを特徴とする高沸点
、高芳香族溶剤の製造方法。(4) The raffinate after recovering normal paraffin from the kerosene fraction is reformed in the first reforming step, then the fraction below 220°C is separated by distillation from the resulting product oil, and the fraction is transferred to the second reforming step. A method for producing a high boiling point, highly aromatic solvent, which comprises reforming in the reforming step and then distilling and separating a fraction in the range of 185 to 220°C.
ラフィネートを第１の改質工程で改質し、次いで得られ
た生成油から２４５℃以下の留分を蒸留分離し、当該留
分を第２の改質工程で改質した後、１８５〜２２０℃の
範囲の留分を蒸留分離することを特徴とする高沸点、高
芳香族溶剤の製造方法。(5) The raffinate after recovering normal paraffin from the kerosene fraction is reformed in the first reforming step, and then the fraction below 245°C is separated by distillation from the resulting product oil, and the fraction is transferred to the second reforming step. A method for producing a high boiling point, highly aromatic solvent, which comprises reforming the solvent in the reforming step and then distilling and separating a fraction in the range of 185 to 220°C.
ラフィネートを第１の改質工程で改質し、次いで得られ
た生成油から２４５℃以下の留分を蒸留分離し、当該留
分を第２の改質工程で改質した後、２０５〜２４５℃の
範囲の留分を蒸留分離することを特徴とする高沸点、高
芳香族溶剤の製造方法。(6) The raffinate after recovering normal paraffin from the kerosene fraction is reformed in the first reforming step, and then the fraction below 245°C is separated by distillation from the resulting product oil, and the fraction is transferred to the second reforming step. A method for producing a high boiling point, highly aromatic solvent, which comprises reforming the solvent in the reforming step and then distilling and separating a fraction in the range of 205 to 245°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6608289A JPH02247293A (en) | 1989-03-20 | 1989-03-20 | Production of high boiling point, high aromatic solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6608289A JPH02247293A (en) | 1989-03-20 | 1989-03-20 | Production of high boiling point, high aromatic solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02247293A true JPH02247293A (en) | 1990-10-03 |
Family
ID=13305577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6608289A Pending JPH02247293A (en) | 1989-03-20 | 1989-03-20 | Production of high boiling point, high aromatic solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02247293A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001164291A (en) * | 1999-12-09 | 2001-06-19 | Japan Energy Corp | Cleaning liquid composition for wax and pitch |
| JP2002097494A (en) * | 2000-09-22 | 2002-04-02 | Japan Energy Corp | Detergent for chemical plant and its cleaning method |
| JP4530381B2 (en) * | 1999-12-08 | 2010-08-25 | 株式会社ジャパンエナジー | Cleaning liquid composition |
-
1989
- 1989-03-20 JP JP6608289A patent/JPH02247293A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4530381B2 (en) * | 1999-12-08 | 2010-08-25 | 株式会社ジャパンエナジー | Cleaning liquid composition |
| JP2001164291A (en) * | 1999-12-09 | 2001-06-19 | Japan Energy Corp | Cleaning liquid composition for wax and pitch |
| JP4530382B2 (en) * | 1999-12-09 | 2010-08-25 | 株式会社ジャパンエナジー | Washing liquid composition for wax and pitch |
| JP2002097494A (en) * | 2000-09-22 | 2002-04-02 | Japan Energy Corp | Detergent for chemical plant and its cleaning method |
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