JPH03178936A - Production of 2-methylnaphthalene - Google Patents
Production of 2-methylnaphthaleneInfo
- Publication number
- JPH03178936A JPH03178936A JP1317526A JP31752689A JPH03178936A JP H03178936 A JPH03178936 A JP H03178936A JP 1317526 A JP1317526 A JP 1317526A JP 31752689 A JP31752689 A JP 31752689A JP H03178936 A JPH03178936 A JP H03178936A
- Authority
- JP
- Japan
- Prior art keywords
- methylnaphthalene
- fraction
- fraction containing
- reforming reaction
- methylnaphthalenes
- 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
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000006057 reforming reaction Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 6
- -1 polyethylene naphthalenedicarboxylate Polymers 0.000 abstract description 3
- 238000002407 reforming Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001225 polyester resin Polymers 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000003350 kerosene Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910017464 nitrogen compound Inorganic materials 0.000 description 5
- 150000002830 nitrogen compounds Chemical class 0.000 description 5
- 150000003464 sulfur compounds Chemical class 0.000 description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- OVRFMMLOGHJZLA-UHFFFAOYSA-N 2-methyl-2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)C(C)C=CC2=C1 OVRFMMLOGHJZLA-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-RHRFEJLCSA-N 2-methylnaphthalene Chemical class C1=CC=[14CH]C2=CC(C)=CC=C21 QIMMUPPBPVKWKM-RHRFEJLCSA-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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006011 modification reaction Methods 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
- 229910052684 Cerium Inorganic materials 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011820 acidic refractory Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 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
- 238000010924 continuous production Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 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
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000000746 purification Methods 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
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052718 tin Inorganic materials 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業−にの利用分野１
本発明は、１−メチルナフタレンを含む留分から２−メ
チルナフタレンを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for producing 2-methylnaphthalene from a fraction containing 1-methylnaphthalene.
この２−メチルナフタレンは染料、医薬品等の中間体と
して従来より用いられており、さらに、最近は、メチル
アルコールとの反応により、２゜６−シメチルナフタレ
ンとすることができ、ポリエチレンナフタレ−）・等ポ
リエステル系樹脂の原料となるナフタレンジカルボン酸
の製造中間体としても注目を集めている。This 2-methylnaphthalene has traditionally been used as an intermediate for dyes, pharmaceuticals, etc., and recently it has been made into 2゜6-dimethylnaphthalene by reaction with methyl alcohol, and polyethylene naphthalene. ), etc. It is also attracting attention as an intermediate in the production of naphthalene dicarboxylic acid, which is a raw material for polyester resins.
〔従来の技術］
２−メチルナフタレンの工業的な製造方法としては、石
炭の乾留により生成するタール分を蒸留し、得られるメ
チルナフタレン留分よりインドール分を取り除いた後、
晶析する方法が広く採用されている。[Prior Art] As an industrial method for producing 2-methylnaphthalene, the tar component produced by carbonization of coal is distilled, the indole component is removed from the resulting methylnaphthalene fraction, and then the indole component is removed.
Crystallization methods are widely used.
かかる方法により得られた２−メチルナフタレン中には
、高濃度の硫黄化合物や窒素化合物が含まれ、これを原
料として各種の化合物を合成する際、触媒の劣化を生じ
る場合があり、硫１７化合物や窒素化合物の含有量の少
ない高純度の２−メチルナフタレンが望まれていた。2-Methylnaphthalene obtained by this method contains high concentrations of sulfur compounds and nitrogen compounds, and when various compounds are synthesized using this as a raw material, deterioration of the catalyst may occur. High purity 2-methylnaphthalene with a low content of nitrogen compounds and nitrogen compounds has been desired.
本発明者は、かかる要請に基づき、脱流打曲を接触改質
してメチルナフタレンを回収することにより、高品質の
メチルナフタレンを製造する方法を提案した（特開平１
−１６８ Ｓ ２９ シー）。Based on this request, the present inventor proposed a method for producing high-quality methylnaphthalene by recovering methylnaphthalene by catalytically reforming deflow percussion (Japanese Patent Application Laid-Open No.
-168 S 29 Sea).
［発明が解決しようとする課題］
本発明者は、Ｌ記方法についてさらに研究を進めた結果
、１−メチルナフタレンを改質反応したところ、驚くべ
きことに、異性化反応を起こし、２−メチルナフタレン
を生成することか分かった。[Problems to be Solved by the Invention] As a result of further research on the method described in L, the present inventor conducted a modification reaction on 1-methylnaphthalene, and surprisingly, an isomerization reaction occurred, resulting in 2-methyl It turned out that naphthalene was produced.
本発明は、かかる知見に」、Ｉ；づきなされたもので、
本発明の目的は、メチルナフタレン類を含む留分から２
−メチルナフタレンを効率良く製造する方法を提供する
ことにある。The present invention has been made based on this knowledge.
The purpose of the present invention is to extract 20% from a fraction containing methylnaphthalenes.
- To provide a method for efficiently producing methylnaphthalene.
［課題を解決するための手段］
本発明は、１−メチルナフタレンを含む留分を改質度ｂ
ｔ：することからなり、またさらには、メチルナフタレ
ン類を含む留分から２−メチルナフタレ〉・を分離回収
し、分離回収後の残液を改質反応に供することからなる
２−メチルナフタｌノンの製造方法である。[Means for Solving the Problems] The present invention provides a method for modifying a fraction containing 1-methylnaphthalene to a degree of modification b.
t: Production of 2-methylnaphthalone, which further comprises separating and recovering 2-methylnaphthalene from a fraction containing methylnaphthalenes and subjecting the residual liquid after separation and recovery to a reforming reaction. It's a method.
上記１−メチルナフタレンを含む留分とは、メチルナフ
タレンか合まれでおれば、特に支障はないか、１〜メチ
ルナフタレンを２０重１１ｔ％以１；含むものか、２−
メチルナフタレンの動帯的な製造の上から好ましい。The above-mentioned fraction containing 1-methylnaphthalene means whether there is no particular problem as long as methylnaphthalene is not included, or whether it contains 20% by weight or more than 11t% of 1-methylnaphthalene, or 2-methylnaphthalene.
It is preferable from the viewpoint of continuous production of methylnaphthalene.
また、この１−メチルナフタレンを含む留分としては、
メチルナフタレン類を含む留分から２メヂルナフタレン
を分離回収し、分離回収後の残液を用いると良い。この
メチルナフタレン類を含む留分とは、２３０〜２５０℃
の沸点範囲にある成分を含むもので、メチルナフタレン
類を７０重量％以上含む留分が、好ましい。これらの留
分は、右炭タール、或は流動接触分解プロセスのサイク
ル泊を蒸留分離して得られた留分を用いることかできる
（特開昭６０−６９０４２号公報参照）。しかし、これ
らの留分中には、２、−メチルナフタレンを吸着分離す
る際のゼオラ゛イＩ・や改質反応の際の触媒の寿命を著
しく短くする窒素化合物や硫黄化合物が鳥濃度で含まれ
ている３、従って、これらを用いる場合は、これらの処
理の前に、この窒素及び硫黄化合物の低減処理を行う必
要がある。また、ナフサ留分を改質反応させたリホーメ
ートの重質留分にも、メチルナフタレン類が含まれてお
り、このリホーメートを蒸留分離して得た留分も用いる
ことができる。この留分は、窒素化合物や硫汝化合物の
含有量が少ないので好ましい。さらに、灯？１１１留分
を改質反応さぜた改質ｉ＋Ｉ＋中にメチルナフタレン類
が多く含まれており、これを用いると、上記ナフサから
得られた留分より、効率良く、メチルナフタレン類を回
収することができ、また、窒素化合物や硫黄化合物の含
有量が少なく、特に好ましい。In addition, as a fraction containing this 1-methylnaphthalene,
It is preferable to separate and recover 2-methylnaphthalene from the fraction containing methylnaphthalenes, and use the residual liquid after separation and recovery. The fraction containing this methylnaphthalene is 230-250℃
A fraction containing components having a boiling point range of 70% by weight or more of methylnaphthalenes is preferred. As these fractions, it is possible to use right coal tar or a fraction obtained by distilling and separating the cycle residue of a fluid catalytic cracking process (see Japanese Patent Laid-Open No. 60-69042). However, these fractions contain high concentrations of zeolite I, which is used to adsorb and separate 2,-methylnaphthalene, and nitrogen and sulfur compounds that significantly shorten the life of the catalyst in the reforming reaction. Therefore, when these are used, it is necessary to perform a reduction treatment for nitrogen and sulfur compounds before these treatments. Furthermore, the heavy fraction of reformate obtained by subjecting the naphtha fraction to a reforming reaction also contains methylnaphthalenes, and the fraction obtained by distilling and separating this reformate can also be used. This fraction is preferable because it has a low content of nitrogen compounds and sulfur compounds. Furthermore, the light? A large amount of methylnaphthalenes are contained in the reformed i+I+ obtained by mixing the 111 fraction with a reforming reaction, and by using this, methylnaphthalenes can be recovered more efficiently than the fraction obtained from the above naphtha. It is particularly preferable because it has a low content of nitrogen compounds and sulfur compounds.
このメチルナフタレン類を含む留分からゼオライト等に
よる吸着分離法、晶析法、錯化合物形成による分離法等
の公知の手段を用いることにより、２−メチルナフタレ
ンを分離回収することができ、この回収残液を、改質反
応に供すると良い。2-Methylnaphthalene can be separated and recovered from this fraction containing methylnaphthalene by using known means such as adsorption separation using zeolite, crystallization, and separation by complex compound formation. It is preferable to subject the liquid to a reforming reaction.
−・方、改質反応は、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。この場合、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、すす、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〜
５０ ｋｇ／ ｃｎ＋の圧力、液空間速度（ＬＨ８Ｖ）
Ｏｊ〜３ ｈ −’、水素／油モル比０．５〜２０の条
件下に行うことができる。- For the reforming reaction, a catalytic reforming method which is widely used as a method for producing high octane gasoline from naphtha fraction etc. can be adopted. In this case, for example, a catalyst in which platinum is supported on alumina as a carrier, or rhenium, germanium, soot, iridium, ruthenium, etc. in addition to platinum, is used at a temperature of 400 to 550°C, 1 to
50 kg/cn+ pressure, liquid hourly velocity (LH8V)
It can be carried out under the conditions of Oj~3h-' and a hydrogen/oil molar ratio of 0.5~20.
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
ム等の金属類を倉荷させるかあるいは担持させた触媒等
を用いて、２５０〜７００℃の温度、１〜１００ｋｇ／
ｃボの圧力、０．１〜２０ｈ−”の■、ＨＳ Ｖ、水素
／油モル比０．５〜２０の条件下に行なわせることもで
きる。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。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 /
The reforming reaction can also be carried out under the following conditions: a pressure of 0.1 to 20 hours, a hydrogen/oil molar ratio of 0.5 to 20, and a hydrogen/oil molar ratio of 0.5 to 20. Although a reactor 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.
この改質された２−メチルナフタレンに富む改質ｉ１ｔ
＋からゼオライト等による吸着分離法、晶析法、錯化合
物形成による分離法等の公知の手段を用いることにより
、２−メチルナフタレンを分離回収すると良い。This modified 2-methylnaphthalene-rich modification ilt
It is preferable to separate and recover 2-methylnaphthalene from the 2-methylnaphthalene by using known means such as an adsorption separation method using zeolite, a crystallization method, a separation method by forming a complex compound, or the like.
〔実施例］
次に、本発明の好ましい実施態様の−っである、灯油留
分を出発原料として、これを改質反Ｌｉ；を行い、この
改質油から２−メチルナフタレンを製造する方法につい
て、具体的に述べる。[Example] Next, a method of producing 2-methylnaphthalene from this reformed oil by using a kerosene fraction as a starting material and subjecting it to reforming with Li, which is a preferred embodiment of the present invention. I will discuss this in detail.
この場合の灯ｉ＋ｂ留分としては、蒸留分離操作により
１．５０〜３００℃の温度範囲で留出する留分を用いる
ことができ、圧力１（を常圧蒸留して得られた直留の灯
η１１留分の他、右曲の各留分、戊清等の熱分解、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。この灯油留分け、好ま
しくは、硫Ｉｊ分及び窒素用が、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〜／１．３０℃の温度、１０〜２００ｋｇ
／ｃｍ！（７）作力、液空間速度（Ｉ、Ｈ３Ｖ）０．１
〜］、５ｈ −’水素循環量５０−１４００ Ｎｍ／ｋ
１２の条件下で脱硫した脱硫１ｌｌｌ＋を用いることが
好ましい。尚、この灯カ１１留分は、上記の他、−［、
記灯油留分からノルマルパラフィンを回収したラフィネ
ートを用いても良ぐ、この場合は、改質反応条件をマイ
ルドにしても、メチルナフタレン類の生成量を多くする
、二とができる。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線素アダクトによる分
離方法を用いて行なうことかできる。このラフイネ−１
・は、ノルマルパラフィンを５０〜９５％程度の１す１
収串で同数除去したもので充分である。In this case, as the lamp i+b fraction, a fraction distilled in a temperature range of 1.50 to 300°C by distillation separation operation can be used. In addition to the lamp η11 fraction, each fraction of the right curve, fractions in the above boiling point range obtained by thermal cracking such as Bosei, catalytic cracking, hydrocracking, alkylation, and other purification treatments may also be used. It goes without saying that this kerosene distillate preferably has a sulfur Ij content and a nitrogen content of 50 ppm or less. Conditions, for example, using a catalyst in which one or more of cobalt, nickel, molybdenum, tungsten, etc. is supported on a carrier such as alumina or silica-alumina, a temperature of 250 to 1.30°C, and a weight of 10 to 200 kg.
/cm! (7) Working force, liquid space velocity (I, H3V) 0.1
~], 5h -'Hydrogen circulation amount 50-1400 Nm/k
It is preferable to use desulfurized 1llll+ desulfurized under the conditions of No. 12. In addition to the above, these 11 fractions of lamps include -[,
Raffinate obtained by recovering normal paraffins from the kerosene fraction may be used. In this case, even if the reforming reaction conditions are made mild, the amount of methylnaphthalenes produced can be increased. This removal of normal paraffins can be carried out using an adsorption separation method using zeolite or a separation method using a linear adduct. This rough uine-1
・I use 50 to 95% normal paraffin.
It is sufficient to remove the same number with a skewer.
この灯油留分の改質反応は、上述した接触改質方法の触
媒及び条件が採用できる。このようにして得られる灯油
留分の改質油から蒸留、溶剤抽出、通常の晶析法或は圧
力晶析法等によりメチルナフタレン類を高濃度に含む留
分を回収する。回収は、蒸留による方法が経済的で好ま
しく、２３０〜２５０℃の留分を採取することにより、
メチルナフタレン類を高濃度含有した留分を得ることが
できる。For the reforming reaction of this kerosene fraction, the catalyst and conditions of the catalytic reforming method described above can be employed. From the reformed oil of the kerosene fraction thus obtained, a fraction containing a high concentration of methylnaphthalenes is recovered by distillation, solvent extraction, ordinary crystallization method, pressure crystallization method, etc. For recovery, a distillation method is economical and preferable, and by collecting a fraction at 230 to 250°C,
A fraction containing a high concentration of methylnaphthalenes can be obtained.
このメチルナフタレン類を含む留分からゼオライト等に
よる吸着分離法、晶析法、錯化合物形成による分離法等
の手段を用いることにより、２−メチルナフタレンを分
離回収する。From this fraction containing methylnaphthalenes, 2-methylnaphthalene is separated and recovered by means such as an adsorption separation method using zeolite, a crystallization method, a separation method using complex compound formation, or the like.
次に、この回収残液を、改質反応に供する。Next, this recovered residual liquid is subjected to a reforming reaction.
この場合の改質反応も、前述した触媒及び条件がそのま
ま適用できる。特には、この残液を、先の改質反応の原
料として供給されている打力１１留分に混合して、改質
反応に供するようにすることが、装飲の運転操作上簡便
で何ましい。For the reforming reaction in this case, the catalyst and conditions described above can be applied as they are. In particular, it is convenient and convenient for the operation of the charging and drinking system to mix this residual liquid with the 11 fractions of striking power supplied as the raw material for the reforming reaction and to provide it for the reforming reaction. Delicious.
次に、本発明の効果を明確にするために、実験例を示す
。Next, an experimental example will be shown in order to clarify the effects of the present invention.
（実験例１）
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
る脱硫灯油留分を原料とし、アルミナ担体に白金を０．
２重量％１′１１持した接触改質触媒を用いて、圧力を
２５ｋｇ／ｃｎｔ、温度を４９０℃、Ｌ ＨＳ Ｖを０
．８ｈ−”、水素７泊をモル比で６の条件下で、改質反
応させた。この改質油を常圧蒸留し、２３０〜２５０℃
の留分を採取した結果、第２表に示す組成のメチルナフ
タレン混合物が得られた。(Experimental Example 1) A desulfurized kerosene fraction having the properties shown in Table 1 obtained by hydrodesulfurizing a kerosene fraction was used as a raw material, and 0.0% platinum was added to an alumina carrier.
Using a catalytic reforming catalyst containing 2% by weight of 1'11, the pressure was 25 kg/cnt, the temperature was 490°C, and the L HS V was 0.
．． A reforming reaction was carried out under the conditions of 8 h-'' and 7 h of hydrogen at a molar ratio of 6. This reformed oil was distilled under atmospheric pressure and heated to 230-250°
As a result of collecting the fraction, a methylnaphthalene mixture having the composition shown in Table 2 was obtained.
（以下余白）
第
１
表
第
表
１
（実験例２）
１−メチルナフタレン９９．６ｗｔχ、２−メチルナフ
タレン０．４ｗｔ％からなる原料を用い、実験例１と同
じ触媒を用いて、圧力を２５ ｋｇ／ｃｎｔ、 ＬＨ
Ｓ Ｖを０．８ｈ−”、水素／油をモル比で６の条件下
、第４表に示した温度で改質反応した結果、第４表に示
す組成のメチルナフタレン混合物が得られた。(Leaving space below) Table 1 Table 1 (Experimental Example 2) Using raw materials consisting of 99.6 wt% 1-methylnaphthalene and 0.4 wt% 2-methylnaphthalene, and using the same catalyst as in Experimental Example 1, a pressure of 25% was used. kg/cnt, LH
As a result of the reforming reaction at the temperature shown in Table 4 under the conditions of SV of 0.8 h-'' and hydrogen/oil molar ratio of 6, a methylnaphthalene mixture having the composition shown in Table 4 was obtained.
第４表
これらの結末から明らかなよう（こ、１−メチルナフタ
レンを含存する留分を改質反応させることにより、２−
メチルナフタｌノンを得ることがで・きる。Table 4 As is clear from these results (by subjecting the fraction containing 1-methylnaphthalene to a reforming reaction, 2-methylnaphthalene
Methylnaphthalone can be obtained.
１Ｌ）
〔発明の効果〕
本発明は、ｌ−メチルナフタレンから２−メチルナフタ
レンを簡便に製造でき、さらにメチルナフタレン類を含
む留分から２−メチルナフタレンを分離回収し、分離回
収後の残液を改質反応に供するようにすると、極めて動
帯良く２−メチルナフタｌノンを製造できるという格別
の効果を有する。1L) [Effects of the Invention] The present invention allows 2-methylnaphthalene to be easily produced from l-methylnaphthalene, and furthermore, 2-methylnaphthalene is separated and recovered from a fraction containing methylnaphthalenes, and the residual liquid after separation and recovery is When subjected to a reforming reaction, 2-methylnaphthalone can be produced in an extremely efficient manner, which is a special effect.
Claims (2)
ことを特徴とする２−メチルナフタレンの製造方法。(1) A method for producing 2-methylnaphthalene, which comprises subjecting a fraction containing 1-methylnaphthalene to a reforming reaction.
フタレンを分離回収し、分離回収後の残液を改質反応に
供することを特徴とする２−メチルナフタレンの製造方
法。(2) A method for producing 2-methylnaphthalene, which comprises separating and recovering 2-methylnaphthalene from a fraction containing methylnaphthalenes, and subjecting the residual liquid after separation and recovery to a reforming reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1317526A JPH03178936A (en) | 1989-12-08 | 1989-12-08 | Production of 2-methylnaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1317526A JPH03178936A (en) | 1989-12-08 | 1989-12-08 | Production of 2-methylnaphthalene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03178936A true JPH03178936A (en) | 1991-08-02 |
Family
ID=18089229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1317526A Pending JPH03178936A (en) | 1989-12-08 | 1989-12-08 | Production of 2-methylnaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03178936A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0578265A (en) * | 1990-12-12 | 1993-03-30 | Kawasaki Steel Corp | Production of 2-methylnaphthalene and method for recovering activity of catalyst used therefor |
-
1989
- 1989-12-08 JP JP1317526A patent/JPH03178936A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0578265A (en) * | 1990-12-12 | 1993-03-30 | Kawasaki Steel Corp | Production of 2-methylnaphthalene and method for recovering activity of catalyst used therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW513483B (en) | Catalytic reforming process with three catalyst zones to produce aromatic-rich product | |
| JP2544922B2 (en) | Combined method of hydroreforming and hydroisomerization | |
| EP1893722A1 (en) | Process for increasing production of benzene from hydrocarbon mixture | |
| JP2001098281A (en) | Method for preparation of oil having high viscosity index | |
| US7037422B2 (en) | Process for producing high RON gasoline using CFI Zeolite | |
| KR960004868B1 (en) | Process for production of dimethylnaphthalenes | |
| JP2006518802A (en) | Method for producing high RON gasoline using ATS zeolite | |
| JPH03178936A (en) | Production of 2-methylnaphthalene | |
| JP2520723B2 (en) | Method for producing methylnaphthalene | |
| JPH05310612A (en) | Purification of oil containing methylnaphthalene | |
| JP2520725B2 (en) | Method for producing dimethylnaphthalene | |
| JP2520722B2 (en) | Method for producing methylnaphthalene | |
| JPH01168629A (en) | Production of methylnaphthalenes | |
| JP2520724B2 (en) | Method for producing dimethylnaphthalene | |
| US2981675A (en) | Subsequent treatment of a naphtha reformate to obtain a high octane gasoline | |
| JPH0338532A (en) | Production of dimethylnaphthalene rich in 2,6-isomer | |
| JP3402488B2 (en) | Process for producing a fraction rich in methylnaphthalene and dimethylnaphthalenes | |
| JP6254881B2 (en) | Method for producing xylene | |
| JPH05310611A (en) | Production of 2-methylnaphthalene | |
| JPH02247293A (en) | Production of high boiling point, high aromatic solvent | |
| JPH0639432B2 (en) | Method for producing dimethylnaphthalene | |
| JPH06145672A (en) | Production of fraction containing highly aromatic hydrocarbon | |
| JP2649412B2 (en) | Method for producing 2,6-dimethylnaphthalene | |
| JPH02247291A (en) | Production of solvent with high aromatic content | |
| JPH02247289A (en) | Production of high-boiling solvent with high aromatic content |