Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/42—Platinum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/46—Ruthenium, rhodium, osmium or iridium
  • B01J23/468—Iridium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
  • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
  • B01J29/043—Noble metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
  • B01J29/74—Noble metals
  • B01J29/7469—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J29/7869—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof

Definitions

• the present invention relates to a process for the upgrading of distillates having a boiling point ranging from 100 to 450 °C.
• the process comprises the opening of the ring of the naphthene compounds contained in these distillates to obtain prevalently branched, open-chain paraffinic compounds, mainly having the same number of carbon atoms as the starting naphthene.
• the process is carried out in the presence of a bifunctional catalytic system comprising one or more metals selected from P , Pd, Ir, Ru, Rh and Re, and a silico- aluminate of an acidic nature, selected from a micro- mesoporous silico-alumina having a suitable composition, and a zeolite belonging to the MT group.
• a bifunctional catalytic system comprising one or more metals selected from P , Pd, Ir, Ru, Rh and Re, and a silico- aluminate of an acidic nature, selected from a micro- mesoporous silico-alumina having a suitable composition, and a zeolite belonging to the MT group.
• the present invention also relates to particular catalytic compositions.
• the production of clean fuels for use in new generation engines which reduce exhaust emissions, is one of the main problems of the refining industry.
• the selective opening of the naphthene ring is, on the other hand, much more complex.
• the opening of the naphthene ring can be effected according to two mechanisms: breakage of the C-C bond by means of a mechanism of the carbo-cationic type; this mechanism, operating with classical bifunctional catalysts consisting of a metal which has a hydro/dehydrogenating function on an acidic support, is generally characterized by a low selectivity, due to the presence of dealkylation reac- tions and the secondary cracking of the alkanes formed; breakage of the C-C bond of the ring via hydro- genolysis, catalyzed by a metal such as platinum, rhodium or iridium, on a non-acidic support.
• US 5,463,155 describes a combined process for increasing the content of isoparaffins in naphtha, which comprises : a treatment step of naphtha, giving a paraffin- enriched intermediate mixture, effected with a non- acidic catalyst comprising at least one metal of the platinum group and a support selected from metal oxides and large-pore zeolites, wherein the support is made non-acidic by means of suitable impregnation or ion exchange treatment with solutions of alkaline or alkaline-earth salts; a second step in which the mixture thus obtained is subjected to isomerization in the presence of an acid catalyst containing at least one metal of the platinum group .
• US 5,382,731 describes a two-step process in which the charge is put in contact, in the first reactor, with a ring-opening catalyst, consisting of a component which has a hydro-dehydrogenating function and an acidic solid con- sisting of zirconia modified with tungstate.
• the second reactor operates in such a way as to favour isomerization.
• the catalyst consists of platinum deposited on alumina and the reaction takes place in the presence of a chlorinated compound.
• US 5,763,731 describes a process for selective ring-opening in compounds of the naphthene type, giving paraffinic-type compounds.
• the process uses catalysts containing a metal selected from Ir, Ru or their mixtures and is capable of reducing the number of cyclic structures in the product by the opening of the ring, with- out dealkylation of the alkyl substituents linked to these cycles.
• a metal selected from Ir, Ru or their mixtures
• the paraffins thus obtained prove to be mainly linear or with low branchings.
• This patent also specifies that the use of platinum on a Y-type zeolitic support leads to very low selectivities towards the opening of the ring.
• EP 875288 describes a process for the ring-opening of organic compounds containing cycles using a catalyst containing a support selected from alumina, silica, zirconia or their mixtures, a metal selected from Pt, Pd, Rh, Re, Ir, Ni, cobalt and their mixtures, and a metal selected from W, Mo, La and rare earth metals.
• the product obtained mainly contains n-paraffins, whereas skeleton isomeriza- tion, cracking and dehydrogenation reactions are substantially suppressed.
• the reaction is effected on bifunctional catalysts, the splitting of the C-C bond present in paraffinic chains or naphthene compounds takes place by the formation
• the patent EP 582347 describes a bifunctional catalyst which comprises : a) a component of an acidic nature consisting of a gel of silica and alumina amorphous to X-rays, having a molar ratio Si0 2 /Al 2 0 3 ranging from 30 to 500, a surface area ranging from 500 to 1,000 m 2 /g, with a porosity of 0.3 to 0.6 mg/g, a pore diameter prevalently within the range of 10-30
• This material is capable of catalyzing the hydro- isomerization of n-paraffins .
• the Applicant has now surprisingly found a process for obtaining the opening of the naphthene rings to give paraf- finic compounds, preferably branched, in a single reaction step, with high conversions and selectivities, using catalytic compositions having suitably calibrated acidity characteristics. Contrary to what is currently known, it has been found that by the appropriate selection of the acidic component and metal, it is possible to obtain, also in the case of a bifunctional catalyst, conversions of naphthene rings to paraffins with significantly higher selectivities with respect to the known art.
• a first object of the present invention therefore re- lates to a process for the upgrading of distillates having a boiling point ranging from 100 to 450°C, by the ring opening of the naphthene compounds contained in the distillates to give paraffin mixtures, said process consisting in treating said distillates, in the presence of hydrogen, with a catalytic system comprising: a) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re b) a silico-aluminate of an acidic nature selected from a zeolite belonging to the MTW group and a completely araor- phous, micro-mesoporous silico-alumina, having a molar ra- tio Si0 2 /Al 2 0 3 ranging from 30 to 500, a surface area greater than 500 m 2 /g, a pore volume within the range of 0.3-1.3 ml/g, an average pore diameter of less than 40 A.
• the distillates thus treated prove to be enriched in paraffins mainly having the same number of carbon atoms as the starting naphthenes .
• Isoparaffinic compounds prevail in the paraffinic mixtures thus obtained.
• the acid component (b) of the catalytic composition can be selected from zeolites of the MTW type: the MTW group is described in Atlas of zeolite structure types, W.M.Meier and D.H.Olson, 1987, Butterworths .
• ZSM-12 zeolite described in US 3,832,449, is preferably used for the process of the present invention.
• the component of an acidic nature (b) is a silico-alumina
• a preferred aspect is that the Si0 2 /Al 2 0 3 molar ratio ranges from 50/1 to 300/1 and the porosity from 0.4 to 0.5 ml/g.
• MSA Micro-mesoporous, completely amorphous silico- aluminas, useful for the present invention, called MSA, are described in US 5,049,536, EP 659,478, EP 812,804. Their
• XRD spectrum from powders does not have a crystalline structure and does not show any peak.
• Catalytic compositions which can be used in the pres- ent invention, in which the acid component is a silico- alumina of the MSA type, are described in EP 582,347.
• the metallic component of the catalytic compositions used in the process of the present invention is selected from Pt, Pd, Ir, Ru, Rh, Re and their mixtures.
• the metal is platinum, irid- ium or their mixtures.
• the metal or mixture of metals is preferably in a quantity ranging from 0.1 to 5% by weight with respect to the total weight of the catalytic composition, and preferably ranges from 0.3 to 1.5%.
• the weight percentage of the metal, or metals refers to the content of metal expressed as a metallic element; in the end-catalyst, after calcination, said metal is in the form of an oxide.
• the catalytic compositions containing one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re, and, as acidic component completely amorphous micro-mesoporous silico- aluminas of the MSA type, are new and are a particular as- pect of the present invention.
• the catalyst is activated by means of the known techniques, for example by means of a reduction treatment, and preferably by drying and subsequent reduction.
• the drying is effected in an inert atmosphere at temperatures ranging from 25 to 100°C, whereas the reduc- tion is obtained by thermal treatment of the catalyst in a reducing atmosphere (H 2 ) at a temperature ranging from 300 to 450°C.
• the acidic component (b) of the catalyst adopted in the process of the present invention can be used as such or in extruded form with traditional binders, such as for example aluminum oxide, bohemite or pseudo-bohemite .
• the acidic component (b) and the binder can be premixed in weight ratios ranging from 30:70 to 90:10, preferably from 50:50 to 70:30.
• the product obtained is consolidated in the desired end-form, for example in the form of extruded pellets or tablets.
• the metal phase (a) of the catalyst this can be introduced by means of impregnation or ion ex- change.
• the acidic component (b) also in extruded form, is wetted with an aqueous solution of a compound of the metal, operating, for example, at room temperature, and at a pH ranging from 1 to 4.
• the aqueous solution preferably has a concentration of the metal expressed as g/1 ranging from 0.2 to 2.0.
• the resulting product is dried, preferably in air, at room temperature, and is calcined in an oxidizing atmosphere at a temperature ranging from 200 to 600°C.
• the acidic compo- nent (b) is suspended in an alcohol solution containing the metal. After impregnation, the solid is dried and calcined.
• the acidic component (b) is suspended in an aqueous solution of a complex or salt of the metal, operating at room temperature and at a pH ranging from 6 to 10.
• the impregnation is carried out as follows: the acidic component (b) , also in extruded form, is wetted with a solution of a compound of a first metal, the resulting product is dried, optionally calcined, and is impregnated with a solution of a compound of a second metal. The product is dried and calcination is then effected in an oxidizing atmosphere at a temperature ranging from 200 to 600°C. Alternatively, a single aqueous solution containing two or more compounds of different metals can be used for contemporaneously introducing said metals.
• the catalytic compositions of the present invention in which the acidic component is a silico-alumina of the MSA type with a pore volume greater than 0.6 ml/g, are new and are a further object of the present invention.
• the catalytic compositions of the present invention in which the acidic component is of the ZSM-12 type, are new and are a further aspect of the present invention.
• the distillates which can be subjected to this upgrading process are mixtures having boiling points within the range of 100 to 450°C. In particular, they can be hydrocarbon cuts selected from naphthas, diesel, kerosene, jet fuel, light cycle oil, HVGO, heavy FCC fraction.
• the process of the present invention is carried out at a temperature ranging from 240 to 380°C, at a pressure ranging from 20 to 70 atm, at a WHSN ranging from 0.5 to 2 hours -1 and a ratio between hydrogen and charge (H 2 /HC) ranging from 400 to 2,000 ⁇ lt/kg. It is preferable to operate at a pressure higher than 40 atm and lower than or equal to 70 atm, whereas the temperature preferably ranges from 240 to 320°C when the acidic component ((b) is a zeolite of the MTW type, whereas it preferably ranges from 300 to 380°C when the acidic component (b) is a silico-alumina.
• Example 1 Preparation of catalyst A: ZSM-12/0.5% Pt a) Preparation of ZSM-12 zeolite 127 grams of tetra-ethyl ammonium hydroxide at 40% by weight, in aqueous solution, are added to 24 grams of de- mineralized water. 4 grams of sodium aluminate at 56% by weight of Al0 3 are then added. The limpid solution thus obtained is poured, under stirring, into 350 grams of Ludox HS 400 colloidal silica. After brief stirring, a homogeneous limpid gel is obtained, which is poured into a 1 litre autoclave made of AISI 316 steel, equipped with an anchor stirrer.
• the gel is left to crystallize under hydro-thermal conditions at 160 °C for 60 hours.
• the autoclave is cooled to room temperature.
• the slurry obtained is homogeneous with a milky appearance.
• the slurry is centrifuged.
• the solid discharged is washed by re- dispersion in water, centrifuged again, dried at 120°C and calcined at 550°C for 5 hours.
• the solid obtained proves to consist of pure ZSM- 12.
• the solid obtained is subsequently exchanged in ammonia form by treatment with a 3 M solution of ammonium' acetate.
• the zeo- lite Upon subsequent calcination at 550 °C for 5 hours, the zeo- lite is obtained in acidic form.
• Example 2 A volume of 200 ml of this solution was added to 30 g of the zeolite prepared as described above, so that all the solid was covered by the solution, to avoid heterogeneity in the platinum distribution.
• the suspension thus obtained was maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
• the solvent was subsequently removed by heating to about 70°C under vacuum.
• the dry product was finally calcined under a stream of air with the following temperature profile 25-350°C in two hours, 360°C for 3 hours.
• a ZSM-12 zeolite is obtained, containing 0.5% by weight of platinum.
• Preparation of catalyst B ZSM-12/1% Pt A quantity of platinum equal to 1% by weight, is deposited on a ZSM-12 zeolite, prepared as described in step (a) of the previous example 1. The same procedure described in step (b) of Example 1 is adopted for the deposition, using 400 ml of the same aqueous solution of hexachloro- platinic acid and 30 g of ZSM-12 zeolite.
• Example 3 Preparation of catalyst C: ZSM-12/l% Pt A quantity of platinum equal to 1% by weight is deposited on a ZSM-12 zeolite prepared as described in the previous Example 1, using an aqueous solution of platinum tetra-amine hydroxide Pt (NH 3 ) 4 (OH) 2 having a platinum concentration of 0.861 g/1. A volume of 180 ml of this solution was added to 15.5 g of ZSM-12 prepared as described in step (a) of the previous Example 1, so that all the solid is covered by the solution, in order to avoid heterogeneity in the platinum distribution.
• Example 4 The suspension thus obtained is maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature. The solvent is subsequently removed by heating to about 70 °C under vacuum. The dry product is finally calcined under a stream of air with the following temperature profile 25-380 °C in two hours, 380°C for 3 hours. A ZSM-12 zeolite is obtained, containing 01% by weight of platinum.
• Example 4 A ZSM-12 zeolite is obtained, containing 01% by weight of platinum.
• Preparation of catalyst D MSA 100/1% Pt a) Preparation of the MSA acidic component 23.5 litres of demineralized water, 19.6 kg of aqueous solution at 14.4% by weight of TPA-OH and 600 g of aluminum tri-isopropoxide are introduced into a 100 litre reactor. The mixture is heated to 60°C and maintained under stirring at this temperature for 1 hour, in order to obtain a limpid solution. The temperature of the solution is then brought to 90°C and 31.1 kg of tetra-ethyl silicate are rapidly added.
• the reactor is closed and the stirring rate is regulated at about 1.2 m/s, the mixture being maintained under stirring for three hours at a temperature ranging from 80 to 90°C, with thermostatic control to remove the heat produced by the hydrolysis reaction.
• the pressure in the reac- tor rises to about 0.2 Mpag.
• the reaction mixture is discharged and cooled to room temperature, obtaining a homogeneous and relatively fluid gel (viscosity 0.011
• the solid Upon X-ray analysis, the solid proves to be sub- stantially amorphous, the XRD spectrum from powders does not have a crystalline structure and does not show any peak.
• the suspension thus obtained was maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
• the solvent was subsequently removed by heating to about 70 °C under vacuum.
• the dry product was finally calcined under a stream of air with the following temperature profile 25- 350°C in two hours, 350°C for 2 hours, 350-400°C in 50 min. , 400 °C for 3 hours.
• a silico-alumina of the MSA type is obtained, containing 1% by weight of platinum.
• Example 5 Preparation of catalyst E: MSA 50/1% Pt a) Preparation of the MSA acidic component 23.5 litres of demineralized water, 19.6 kg of aqueous solution at 14.4% by weight of TPA-OH and 1,200 g of aluminum tri-isopropoxide are introduced into a 100 litre reac- tor. The mixture is heated to 60 °C and maintained under stirring at this temperature for 1 hour, in order to obtain a limpid solution. The temperature of the solution is then brought to 90 °C and 31.1 kg of tetra-ethyl silicate are rapidly added.
• the reactor is closed and the stirring rate is regulated at about 1.2 m/s, the mixture being maintained under stirring for three hours at a temperature ranging from 80 to 90 °C, with thermostatic control to remove the heat produced by the hydrolysis reaction.
• the pressure in the reactor rises to about 0.2 MPag.
• the reac- tion mixture is discharged and cooled to room temperature, obtaining a homogeneous and relatively fluid gel (viscosity
• the solid Upon X-ray analysis, the solid proves to be substantially amorphous, the XRD spectrum from powders does not have a crystalline structure and does not show any peak, b) Deposition of platinum (1.0% by weight of Pt) The same procedure is adopted as described in Example 4, using 400 ml of the same aqueous solution of hexachloro- platinic acid, which are added to 30 g of the solid prepared under point (a) . A silico-alumina of the MSA type is obtained, containing 1% of platinum.
• Example 6 Catalyst F: MSA 50/1% of Pt A quantity of Pt equal to 1% by weight is deposited on an MSA acid component prepared according to step (a) of Example 5, using the same deposition procedure as that described in Example 3: 180 ml of an aqueous solution of Pt (NH 3 ) 4 (OH) 2 are used, whose platinum titer is 0.861 g/1, and added to 15.5 g of MSA acid solid prepared as described in step (a) of Example 5. A silico-alumina of the MSA type is obtained, containing 1% of platinum.
• Example 7 Catalyst G: MSA 50/1% of Pt A quantity of Pt equal to 1.5% by weight is deposited on an MSA acid component prepared according to step (a) of Example 5, using the same deposition procedure as that de- scribed in Example 4 : 400 ml of an aqueous solution of hexachloroplatinic acid, with a platinum concentration of 1.125 g/1, are added to 30 g of MSA acid component. A silico-alumina of the MSA type is obtained, containing 1.5% of Pt.
• Example 8
• Catalyst H MSA 50/1% of Ir
• a volume of 400 ml of this solution is added to 30 g of the solid prepared as described in the previous step (a) , so that all the solid is covered by the solution, in order to avoid heterogeneity in the platinum distribution.
• the suspension thus obtained is maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
• the solvent is subse- quently removed by heating to about 70 °C in a stream of air.
• the dry product is finally calcined under a stream of air with the following temperature profile 25-350°C in two hours, 350°C for 2 hours, 350-400°C in 50 min. , 400°C for 3 hours .
• a silico-alumina of the MSA type is obtained, containing 1% by weight of Ir.
• Example 9 Catalytic test The catalytic tests were carried out on a continuous laboratory plant shown in Figure 1.
• the system consisted of a tubular fixed bed reactor (4) with a useful volume of the charge of 20 cm 3 corresponding to a height of the catalytic bed in the isotherm section of 10 cm.
• the feeding of the charge, contained in the tank (1) and hydrogen to the reac- tor are effected by means of a dosage pump (2) and a mass flow meter, respectively.
• the system is also equipped with two gas lines (air and nitrogen) which are used in the regeneration phase of the catalyst.
• the reactor operates in an equicurrent down flow system.
• the temperature of the re- actor is regulated by means of an oven with two heating elements (3) whereas the temperature control of the catalytic bed is effected by means of a thermocouple (10) positioned inside the reactor.
• the pressure of the reactor is regulated by means of a valve (8) situated downstream of the reactor.
• the reaction products are collected in a sepa- rator (5) which operates at room temperature and atmospheric pressure.
• the products leaving the separator (5) pass into a condenser (6) cooled to 5°C and are subsequently sent to a gas meter (C.L.) (7) and then to the blow-down (B.D.) .
• (9) is the breakage disk.
• the distribution of the products and conversion level are determined by means of mass balance and gas chromatographic analysis of the reaction products.
• Catalysts A, B and C were tested in the process of the present invention, in the equipment described above, using methyl-eyelohexane as substrate. Before being tested, the catalysts were activated as follows : 1) 1 hour at room temperature in a nitrogen stream; 2) 1 hour at 50 °C in a hydrogen stream;
• a volume of 200 ml of this solution was added to 30 g of the zeolite so that all the solid was covered by the solution, to avoid heterogeneity in the platinum distribution.
• the suspension thus obtained was maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
• the solvent was subsequently removed by heating to about 70 °C under vacuum.
• the dry product was finally calcined under a stream of air with the following temperature profile 25-350°C in 2 hours, 360°C for 3 hours.
• a mordenite is obtained, containing 1.0 % by weight of platinum.
• the slurry obtained having a pH value of 11.6, was left to crystallize under hydro-thermal conditions at 180°C for 2 days in an AISI 316 steel autoclave, subjected to a rotating movement.
• the ZSM-23 zeolite at this stage of the synthesis is in soda form, in order to obtain the acidic form, it is subjected to the treatment described hereunder.
• 100 g of ZSM-23 are redispersed in 1000 g of an 0.2 M solution of ammonium acetate.
• the mixture is left under stirring at 40°C for about 3 hours.
• the solid phase is then separated and the operation is repeated twice.
• the solid is finally redispersed in demineralized water for a last washing.
• the damp panel obtained consists of ZSM-23 in ammonia form.
• the solid is dried at 150°C, and is then calcined at 550°C for 5 hours in air, thus eliminating the ammonia and possible present of organic templating agent still blocked.
• deposition of the platinum 1.0 % Pt
• a quantity of platinum equal to 1% by weight is deposited on a ZSM-23 zeolite prepared as described in the previous step (a) , using an aqueous solution of platinum tetra-amine hydroxide Pt (NH 3 ) 4 (OH) 2 , having a platinum concentration of 0.861 g/1.
• a volume of 180 ml of this solution was added to 15.5 g of ZSM-23 prepared as described in the previous step (1) , so that all the solid is covered by the solution, to avoid heterogeneity in the platinum distribution.
• the suspension thus obtained was maintained under stirring for about an hour at room temperature and subsequently degassed by suction under vacuum (about 18 mmHg) at room temperature.
• the solvent was subsequently removed by heating to about 70 °C under vacuum.
• the dry product was finally calcined under a stream of air with the following temperature profile 25-380°C in 2 hours, 380°C for 3 hours.
• a ZSM-23 zeolite is obtained, containing 1% of platinum.
• Example 16 (comparative) Preparation of catalyst M
• a commercial amorphous silico alumina (PK-200 of Kalichemie) is used, having the following characteristics:
• Example 17 (comparative) Catalytic test
• the catalytic tests were carried out as described in Example 9, on the continuous laboratory plant shown in Figure 1. Catalysts I, L and M are tested in the process of the present invention using methyl cyclohexane as substrate. Before being tested the catalysts were activated as fol- lows :
• Example 18 (comparative) In this example, the results obtained in US 5,763,731, Example 11 are indicated as a comparison, wherein an Ir/amorphous Si0 2 -Al 2 0 3 catalyst, containing 0.9% by weight of Ir and having an Si0 2 /Al 2 0 3 ratio of 85/15, is tested in the ring opening of n-butyl-cyclohexane (BCH) .
• BCH n-butyl-cyclohexane
• Example 19 the results obtained in US 5,763,731, Example 7 are indicated as a comparison, wherein a Pt/ECR- 32 catalyst, containing 0.9% by weight of Ir is tested in the ring opening of n-butyl-eyelohexane (BCH) .
• BCH n-butyl-eyelohexane
• the ECR-32 zeolite is described in US 4,931,267 At 275°C and a total LHSV of 2.9, a conversion of BCH of 90.0% is obtained, together with a selectivity of products deriving from the ring opening of 0.01. On comparing these results with those obtained in Example 12, it can be observed that the catalyst containing 1% of Pt and ZSM-12 zeolite of the present invention provides much higher selectivity results, not proportional to the diversity of the substrates .

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