JP2007533807A5

JP2007533807A5 -

Info

Publication number: JP2007533807A5
Application number: JP2007508822A
Authority: JP
Filing date: 2005-04-19
Publication date: 2008-06-05

Description

EP 875288号は、アルミナ、シリカ、ジルコニアまたはこれらの混合物から選ばれた支持体；Pt、Pd、Rh、Re、Ir、Ni、コバルトおよびこれらの混合物から選ばれた金属；および、W、Mo、Laおよび希土類金属から選ばれた金属を含有する触媒を使用する、環を含有する有機化合物の開環方法を記載している。得られた生成物は主としてn-パラフィン類を含有するが、骨格異性体化、クラッキングおよび脱水素化反応は、実質的に抑制されている。
上記反応を二官能性触媒上で実施する場合、パラフィン鎖またはナフテン化合物中に存在するC-C結合の開裂は、カルボカチオンの形成およびその後のβ-開裂反応によって生じる。パラフィン化合物とナフテン化合物間の最も重要な差異は、C-C結合の開裂速度であり、ナフテン化合物の場合は大幅に遅い(Weitkamp, J. and Ernst, S., Catal. Today 19,107 (1994))。この反応性の差異の結果として、生成した生成物のその後のクラッキング反応は、ナフテン環の開環に対する極端に低い選択性をもたらす。
特許EP 582347号は、下記を含む二官能性触媒を記載している。
a) X線に対して非晶質のシリカとアルミナのゲルからなり、30〜500の範囲のSiO₂/Al₂O₃モル比、500〜1,000m²/gの範囲の表面積、0.3〜1.3mg/gの有孔率、主として１〜３ｎｍ（10〜30Å）の範囲の孔径を有する酸性を有する成分；
b) 第VIII族に属する１種上の金属。
この材料は、n-パラフィン類の水素化異性体化を触媒作用し得る。 EP 875288 is a support selected from alumina, silica, zirconia or mixtures thereof; metals selected from Pt, Pd, Rh, Re, Ir, Ni, cobalt and mixtures thereof; and W, Mo, Described is a method for opening a ring-containing organic compound using a catalyst containing a metal selected from La and rare earth metals. The resulting product contains mainly n-paraffins, but skeletal isomerization, cracking and dehydrogenation reactions are substantially suppressed.
When the reaction is carried out on a bifunctional catalyst, the cleavage of the CC bond present in the paraffin chain or naphthene compound occurs by the formation of a carbocation followed by a β-cleavage reaction. The most important difference between paraffinic and naphthenic compounds is the rate of CC bond cleavage, which is much slower for naphthenic compounds (Weitkamp, J. and Ernst, S., Catal. Today 19,107 (1994)). As a result of this reactivity difference, the subsequent cracking reaction of the product produced results in extremely low selectivity for the opening of the naphthenic ring.
Patent EP 582347 describes a bifunctional catalyst comprising:
made of amorphous silica and alumina gel with respect to a) X-ray, SiO ₂ / Al ₂ O ₃ molar ratio in the range of 30 to 500, surface area in the range of 500~1,000m ² / g, 0.3~1.3 an acidic component having a porosity of mg / g, mainly having a pore size in the range of 1 to 3 nm ( 10 to 30 mm ) ;
b) One type of metal belonging to Group VIII.
This material can catalyze the hydroisomerization of n-paraffins.

（発明の開示）
今回、本出願人は、驚くべきことに、好ましくは枝分れしたパラフィン系化合物が単一反応工程において高転換率および選択性でもって得られるナフテン環の開環を得る方法を、適切に標準化した酸特性を有する触媒組成物を使用することによって見出した。現在知られていることとは逆に、酸性成分と金属を適切に選定することにより、二官能性触媒の場合においても、ナフテン環のパラフィン類への転換を既知の技術と対比して有意に高い選択性でもって得ることができることを見出した。
従って、本発明の第１の目的は、100〜450℃の範囲の沸点を有する留出物の、該留出物中に含まれるナフテン化合物のナフテン環を開環させてパラフィン系混合物を得ることによる改質方法に関し、該改質方法は、前記留出物を、水素の存在下に、下記を含む触媒系で処理することからなる：
a) Pt、Pd、Ir、Ru、RhおよびReから選ばれた１種以上の金属；
b) MTW群に属するゼオライトおよび30〜500の範囲のSiO₂/Al₂O₃モル比、500m²/gよりも大きい表面積、0.3〜1.3ml/gの範囲内の孔容積、４ｎｍ（40Å）未満の平均孔径を有する完全非晶質微細メソ多孔質シリコアルミナから選ばれた酸性を有するシリコアルミネート。
そのようにして処理した留出物は、出発ナフテンと同じ炭素原子数を主として有するパラフィン類に富んでいることが判明している。
イソパラフィン系化合物は、そのようにして得られたパラフィン混合物において優勢である。 (Disclosure of the Invention)
The Applicant has now surprisingly properly standardized a method for obtaining a naphthenic ring opening, preferably with branched paraffinic compounds obtained with high conversion and selectivity in a single reaction step. It was found by using a catalyst composition having acid properties. Contrary to what is currently known, the proper selection of the acidic component and the metal makes the conversion of naphthenic rings to paraffins significantly, even in the case of bifunctional catalysts, compared to known techniques. It has been found that it can be obtained with high selectivity.
Accordingly, a first object of the present invention is to obtain a paraffinic mixture by opening a naphthene ring of a naphthene compound contained in the distillate having a boiling point in the range of 100 to 450 ° C. The reforming method comprises treating the distillate in the presence of hydrogen with a catalyst system comprising:
a) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re;
b) MTW zeolite and belonging to the group 30~500 SiO _₂ / Al ₂ O ₃ molar ratio in the range of greater surface area than 500 meters ² / g, pore volume in the range of 0.3~1.3ml / g, 4nm (40Å) Silicoaluminate having acidity selected from fully amorphous fine mesoporous silicoalumina having an average pore size of less than.
The distillate so treated has been found to be rich in paraffins mainly having the same number of carbon atoms as the starting naphthene.
Isoparaffinic compounds are predominant in the paraffin mixture thus obtained.

Claims

A method of reforming a distillate having a boiling point varying from 100 to 450 ° C. by opening a naphthene ring of a compound containing a naphthene ring to obtain a paraffinic mixture, wherein the distillate is converted to hydrogen A reforming process characterized in that it is treated with a catalyst system comprising:
a) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re;
_{_{b), SiO 2 / Al 2}} O 3 molar ratio in the range of zeolite and 30 to 500 belonging to the MTW group, surface area greater than 500 meters ² / g, pore volume in the range of 0.3~1.3ml / g, less than 4 nm Silicoaluminate having acidity selected from fully amorphous fine mesoporous silicoalumina having an average pore size of

The process according to claim 1, wherein the acidic component (b) is ZSM-12 zeolite.

Acidic component (b) The method of claim 1, wherein the silico-alumina having a SiO ₂ / Al ₂ O ₃ molar ratio in the range of 50 / 1-300 / 1.

The process according to claim 1, wherein the acidic component (b) is silicoalumina having a porosity in the range of 0.4 to 0.5 ml / g.

The process according to claim 1, wherein the acidic component (b) is silicoalumina whose XRD spectrum from the powder does not have a crystal structure and does not show any peaks.

The method of claim 1, wherein the metal is platinum, iridium, or a mixture thereof.

The process according to claim 1, wherein the metal or metal mixture is in an amount of 0.1 to 5% by weight, based on the total weight of the catalyst composition.

The process according to claim 7, wherein the metal or metal mixture is in an amount of 0.3-1.5% by weight, based on the total weight of the catalyst composition.

The method of claim 1, wherein the distillate is a hydrocarbon fraction selected from naphtha, diesel, kerosene, jet fuel, light cycle oil, HVGO, FCC heavy fraction.

Performed at temperatures ranging from 240 to 380 ° C, pressures ranging from 2.0 to 7.1 MPa, WHSV ranging from 0.5 to 2 h- ¹ and hydrogen / input ratio (H ₂ / HC) ranging from 400 to 2000 Nlt / kg The method of claim 1.

The method according to claim 10, wherein the acidic component (b) is an MTW type zeolite, the pressure is higher than 4.0 MPa and lower than 7.1 MPa, and the temperature is 240-320 ° C.

The method according to claim 10, wherein the acidic component (b) is silicoalumina, the pressure is higher than 4.0 MPa and lower than 7.1 MPa, and the temperature is 300-380 ° C.

Catalyst composition characterized in that it comprises:
a) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re;
b) zeolites belonging to the MTW group ,
Here, when platinum exists, platinum exists in the quantity of 1-5 mass% with respect to the total mass of a catalyst composition .

Catalyst composition characterized in that it comprises:
a) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re;
_{_{b) 30~500 SiO 2 / Al 2}} O 3 molar ratio in the range of, 500 meters surface area greater than ² / g, greater than 0.6ml / g 1.3ml / g or less of pore volume, average pore diameter of less than 4 nm, Fully amorphous fine mesoporous silicoalumina having an XRD spectrum from a powder that has no crystal structure and does not show any peaks.

Catalyst composition characterized in that it comprises:
a) one or more metals selected from Ir, Ru , Rh and Re;
b) the range of 30-500 of SiO ₂ / Al ₂ O ₃ molar ratio greater surface area than 500 meters ² / g, pore volume in the range of 0.3 and 1.3 ml / g, an average pore diameter of less than 4 nm, the crystal structure Fully amorphous fine mesoporous silicoalumina having an XRD spectrum from a powder that does not have and does not show any peaks.

The catalyst according to claim 13, 14 or 15, comprising subjecting the acidic component (b) to impregnation or ion exchange with a solution of a compound of one or more metals selected from Pt, Pd, Ir, Rh and Re. A method for producing the composition.