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
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/54—Hydrogenation of the aromatic hydrocarbons 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
  • 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
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J29/166—Y-type faujasite
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/13—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation with simultaneous isomerisation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
  • C07C2529/14—Iron group metals or copper

Definitions

• the new catalyst exhibits an excellent hydrogenative ring opening activity.
• the present invention relates to a process for the hydrogenative ring opening of polycyclic hydrocar-' bons.
• it is concerned with a process for the hydrogenative ring opening of polycyclic hydrocarbons or heavy hydrocarbon oils containing a large amount of polycyclic hydrocarbons which comprises contacting these hydrocarbon materials with a novel catalyst having a high activity under highly pressurized hydrogen.
• Such type of catalyst have, heretofore, been used in hydrocracking by which gasoline with a high octane rating is to be produced.
• the hydrocracking process comprises subjecting heavy oils, particularly gas oil fractions to cracking under pressurized hydrogen, and the principal reactions involved therein are chain cleavage and isomerization of paraffins and hydrogenation and subsequent ring opening of aromatics contained therein.
• Such reactions may be useful as a pre-treatment means in, for example, thermal-cracking of heavy oils by which raw materials for chemicals are to be produced.
• the present invention relates to a process for the production of monocyclic aromatics and alkyl naphthenes with a high yield from hydrocarbons containing a large amount of fused-ring aromatics and the desulfurization of said hydrocarbon fractions in the production of monocyclic aromatic and alkyl naphthenes by effecting the hydrogenative ring opening under pres surized hydrogen in the presence of a catalyst with hydrocracking metals Ni, W and V supported on a carrier of zeolite Y with nickel ion exchanged therewith.
• the process for the conversion of hydrocarbon fractions containing polycyclic aromatic hydrocarbon is characterized in that the catalyst hydrogenative ring opening of hydrocarbon fractions containing at least 10% (by weight) polycyclic aromatic hydrocarbons is carried out in the presence of a catalyst comprising a carrier of Y-type zeolite, at least 60% (mol) of the sodium ions contained in said zeolite having'bee'n exchanged with nickel ion, supported thereon l to 25% nickel, 1 to 20% tungsten and 0.1 to 5% vanadium based on the weight of the carrier these metals.
• the distinctive characteristics of the present invention are that the zeolite Y which has undergone exchange with nickel ion is used as a carrier and vanadium (and nickel and tungsten) is contained as a catalyst metal component, and for such characteristic, the catalyst of the present invention results in a great improvement in hydrogenative ring opening activity (see the comparative Examples as hereinafter described).
• Catalyst 1. kind of Catalyst (See, D. W. Breck: Molecular Sieve Zeolites, Advances in chemistry Series 101, Am. chem. Soc. Washington D.C.(l97l)).
• the catalyst used in the present invention is required to have nickel which substitutes for sodium ions in' a zeolite carrier and also nickel supported on the carrier.
• the catalyst according to the present invention may be used in a sulfided form, and it. is usually sulfided in practice.
• the ion exchange operation as stated above is repeated 3 to 6 times using a fresh NH Cl solution at every operation, whereby 90 to 95% of the Na ions contained in the zeolite is replaced by NH, ions.
• the zeolite Y thus exchanged is called NHJY.
• A, predetermined amount of dry zeolite y is subjec't'ed, to ion-exchange treatment in an aqueous solution of salts of nickel.
• Any kind of salts of nickel which are water-soluble may be used.
• Nickel nitrate, nickel chloride and the like are usually used.
• the content of the Ni ions contained in the aqueous solution of nickel salts is usually in the range of from 0.5 to 3.0 timesthat of Na ions..With less amounts of Ni ions, the degree of ion exchange is decreased, so that the number of exchanging operations should be increased.
• the ion ex H change is carried outaccording to the same procedure described'in (i). The repeated ion exchange over 3.
• Ni-Y The zeolite Y-th'us. replaced with Ni ions is called Ni-Y.
• Ni-Nl-h-Y The NH Y ion exchanged according to the procedure described in i. is ion exchanged with Ni ions using the same ion exchange method as that described in (ii).
• the resultant zeolite is called Ni-Nl-h-Y.
• NH Y, Ni--Y or Ni-NH- Y as a used carrier is impregnated with the compounds which are sources of metal components in the form of, preferably, a solution (particularly, an aqueous solution), respectively.
• Nickel, tungsten and vanadium are deposited on the carrier in the weight ratio of l to 25:1 to 20:0.[ to 5, and, preferably, 6 to 20 1 to 10 l to 2, respectively, calculated on the basis of the assumption that the total of the carrier and the metals amounts to 100.
• any compounds, preferably, water soluble compounds such as nickel nitrate, which forms metallic nickel on thermal decomposition, may,
• the nickel nitrate may be used in the form of a slurry.
• any compounds preferably, water-soluble compounds such as ammonium silicotungstate or paratungstate, which form metallic tungsten or tungsten oxides upon thermal decomposition, may be used.
• a source of vanadium any compounds, preferably water-soluble compounds such as ammonium metovanadate, which form metallic vanadium or vanadium oxides may be used.
• These compounds may be used as the sourcesof the metal components of the catalyst in any type of combination without havingappreciable effect on the catalytic performance.
• the supporting of the metal components on the carrier is carried out by mixing an "aqueous solution or slurry of the respective salts of Ni, W and V with the ion exchanged zeolite Y as stated above and evaporating the resulting mixture to dryness.
• the mixing may be carried out by treating the mixture'in a kneader for 0.5 to 5 hours.
• the mixture is then dried in a dryer at a temperature in the order of to 150C; Thereafter, the dried mixture is calcined in an atmosphere of air or an inert gas such as nitrogen, helium, argon and the like in a muffle furnace.
• thecontent is gradually heated from room temperature to a temperature of 200 to 400C and kept at that temperature for 0.5 to 3 hours, after which it is heated at a temperature of 480 to 550C for a further 3 hours.
• the mixture is reduced in a stream of hydrogen at.a temperature of about 350 to 450C for about 0.1 to 5 hours and then pre-sulfided in a stream of hydrogen containing 1 to 15% (by'volume) H 8, CS thiophene and the like.
• This sulfiding is carried out in a stream of hydrogen containing H 8, CS thiophene and the like at a temperature of about 200 to 400C for about 1 to 60 minutes.
• the catalyst is cooled to room temperature in an atmosphere of nitrogen.
• the sulfiding of the catalyst may also be effected by adding a simple organosulfur compound such as thiophene or carbon disulfide at the starting of operation in the hydrocarbon conversion process.
• the catalyst thus obtained may be shaped into a tablet and other shaped products, if desired.
• the shaping may be carried out before the impregnation of the compounds of the catalytic metal component sources, but it is, preferably, carried out after the impregnation, and more preferably after the calcining.
• the shaping may be carried out using a suitable binder such as silica-alumina, if desired.
• reaction conditions of the hydrogenative ring opening of condensed ring aromatic are as follows:
• reaction temperature The temperature at which the reaction is carried out may preferably be any temperature within the range of 250 to 500C, and more preferably 350 to 470C. With higher temperatures gasification is increased, while with lower temperatures conversion is decreased. The optimum temperature may be determined depending upon the feed of charge stocks used.
• the pressure of hydrogen at which the reaction is conducted may be any pressure in the range of 10 to 200 kg/cm, and preferably, 50 to 150 kg/cm.
• LHSV liquid hourly space velocity
• hydrocarbon charge stock used in the present invention is hydrocarbon fractions containing not less than (by weight) and preferably (by weight) of condensed ring aromatic hydrocarbons.
• condensed ring aromatic hydrocarbons as herein used signifies hydrocarbons which contain at least one benzene ring in the structure of the condensed ring and have, preferably, not less than 10 carbon atoms.
• Illustrative examples of such condensed ring aromatic hydrocarbon include naphthalene, methylnaptthalenes, anthracene, phenanthrene, pyrene, acenaphthene, tetralin and the like and alkylderivatives thereof.
• the hydrocarbon fractions containing not less than 10% of condensed ring aromatic hydrocarbons include FCC recycle oil, vacuum gas oil, straight run heavy gas oil, residue of thermal cracking, coal tar gas oil and the like.
• the content of the condensed ring aromatic hydrocarbons present in these hydrocarbon fractions is represented by the weight ratio of aromatic ring forming carbon which is determined from the intensity ratio of aromatic ring constituting hydrogen to other hydrogen by means of a nuclear magnetic resonance (NMR) method.
• NMR nuclear magnetic resonance
• the yield of the monocyclic products is 20% (by weight) with the commercially available catalysts NiW/SiO .Al O suitable for hydrocracking while with the NiWV/NiY catalyst of the present invention the monocyclic products can be obtained with a yield of 80% (by weight).
• the reaction conditions under which the comparative experiments were conducted included a temperature of 450C, a pressure of 80 kg/cm and a LHSV of 2 hr, and the comparative data were mainly taken 2 hours after the a-methylnaphthalene was passed over the catalysts.
• NH -Y (1) 500 g of dry zeolite Y was immersed in 21 of an aqueous solution of 107 g NH Cl in water and then, the zeolite was ion exchange treated with stirring while maintaining the mixture at a temperature of to C. After 3 hours, the resulting mixture was filtered and the resulting exchanged zeolite was washed with water, after which the washed zeolite was again subjected to ion exchange treatment in a fresh NH Cl aqueous solution of the same concentration in the same manner described above. When such ion exchange treatment was repeated 3 times, 73% of Na ions was replaced by NH ions. The product thus obtained is called NH -Y (1).
• the NH Y(l) was baked in a muffle furnace at 500C for 1 hour, and then shaped into a pellet having a size of 5 mmqS by means of a pelletizing machine.
• NH Y( l) After shaping, to 30g of NH Y( l) was added 200cc of an aqueous solution of 37.4 g of nickel nitrate (6 hydrate) and 106g of ammonium paratungstate. The resulting mixture was evaporated to dryness to impregnate the NH;,Y (1) with the solution, and the impregnated NH Y (l) was dried in a dryer at a temperature of 110C for 24 hours. After drying, the dried product was calcined at 550C for 3 hours.
• the catalyst so produced is called Ni W/NH -Y( l
• 30 g of NH Y( 1) after being shaped was impregnated with an aqueous solution containing 37.4 g of nickel-nitrate (6 hydrate), 1.06g of ammonium paratungstate and 0.386 g of ammonium vanadate and calcined according to the same manner as that described above.
• the catalyst so produced is called NiWV/NH Y(2).
• Catalyst preparation procedure (2) In this procedure, the catalyst is prepared by using a direct nickel exchange method which will be given hereunder.
• Ni-exchanged zeolite Y so produced is called Ni- Y( 3).
• NiY(3) was added ml of an aqueous solution containing 6.64 g of nickel nitrate hexahydrate, 0.5297g of silicotungstic acid and 0.1926 g of ammonium metavandate and the resulting mixture was evaporated to dryness to attain the impregnation of Ni, W, and V components.
• the impregnated Ni- -Y(3) was dried at a temperature of 110C for 24 hours, the dried Ni-Y(3) was introduced into a muffle furnace and first calcined ata temperature of 300C for 1 hour, after which the temperature was gradually raised to 500C and calcining was further carried out at that temperature for 3 hours.
• the ground product was shaped into pellets having a size of mm by means of a pelletizing machine.
• the pellets were baked at a temperature of 500C for 1 hour.
• the catalyst so obtained is called NiWV/NiY(3).
• Example 2 scribed in Example 2 and the comparison of catalysts bon oil change. Prior to the reaction, all the catalysts performance was carried out 2 hours after the charge were reduced in a stream of hydrogen at a temperature of 400C for 3 hours, and then cooled in a stream of nitrogen to 300C and sulfided in a stream of a mixture of 10% (by volume) of H 8 and 90 (by volume) of stock was passed over the catalysts.
• the efficiency of the catalysts was compared at undergiven reaction conditions a temperature of 450C, a pressure of 80 kglcm a LHSV of 2 hr, a catalyst amount of 15cc and H /oil 1,000 Nm /K1.
• the com- Table 3 Yield of ring opened parative data were obtained 10 hours after the a- 40 47 methylnaphthalene was passed .over the catalysts. 71
• the results are shown in Table 1. In this connection, 33 g; the yields of monocyclic aromatics and decalin are represented by weight percent based on the weight of Experimental conditionsl g y t g -g empera ure the charge stock. 55 Pressure mks/cm,
• the catalyst preparation procedure and the hydrocarbon conversion process were similar to the catalyst preparation procedure (2) and Example 2, respectively.
• the conditions of .the hydrocarbon conversion process were as follows: Temperature: 450C, pressure: 80 kg/cm, LHSV: 2 hr".
• the data were obtained 1.5 hours after the charge stock was'passed over the catalysts. The results are shown in Table 5.
• the catalyst (NiWV/Ni-Y) of the'present invention which was prepared according to the same procedure as the catalyst preparation procedure (2) as stated above contained 2.2 weight percent sodium, l6.2 weight percent nickel, 1.6 weight percent tungsten and 1.6 weight percent vanadium.
• the commercial catalyst consisted of Ni-W/SiO Metal ion used Yield of rin opened .Al O for use in hydrogenative ring opening and conexchange Exchange pmdum ('nclu mg decal'n) tained 6.5 weight percent nickel and 20.0 weight per- Ni 75 83 cent tungsten, calculated as the respective metal ox- Ca 87 44 ides Al 52 I M 71 50
• the treatment conditions are shown in Tables 7, 8 73 63 and 9. Further, the range of the boiling point of the change stock was determined according to AST- M-D-86-66, and the t e of the h drocarbon was yP y analyzed according to ASTM-D-2425-T.
• Table 7-continued Table 8 Charge oil Heavy gas oil Present 7 Commercialwou- As halt cracked I 100 dist1 late light Present Invention Alkyl benzene 20.4 26. lndan, tetra1in, etc. 1%.
• a process for conversion of a hydrocarbon fraction containing at least 10 by weight of condensedring polycyclic aromatic hydrocarbons which comprises hydrogenative ring opening and hydrocracking of said polycyclic aromatic hydrocarbons by hydrogen into substantially monocyclic aromatics and saturated cyclic hydrocarbons in the presence of a catalyst comprising 1 to 25% of nickel, 1 to 20% of tungsten and 0.1 to 5% of vanadium, based on the total weight of a carrier plus the three metals supported on said carrier, which carrier consists of an NaY zeolite in which more than molar of sodium ions have been exchanged with nickel ions.
• a process according to claim 1 wherein said catalyst comprises 6' to 20% of nickel, 1 to 10% of tungsten and l to 2% of vanadium, based on the total weight of the carrier plus the three metals.
• ammonium ions are provided by a water soluble ammonium salt which yields ammonium ions in an aqueous solution.
• ammonium salt is ammonium chloride.
• nickel salt is selected from the group of nickel chloride and nickel nitrate.

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Citations (8)

• 1973
  • 1973-03-15 JP JP48030205A patent/JPS5742675B2/ja not_active Expired
• 1974
  • 1974-03-09 DE DE2411351A patent/DE2411351A1/de not_active Withdrawn
  • 1974-03-12 US US450395A patent/US3929618A/en not_active Expired - Lifetime
  • 1974-03-14 NL NL7403422A patent/NL7403422A/xx not_active Application Discontinuation
  • 1974-03-14 CA CA194,967A patent/CA1022190A/en not_active Expired
  • 1974-03-15 GB GB1173074A patent/GB1423473A/en not_active Expired
  • 1974-03-15 FR FR7408979A patent/FR2221510B1/fr not_active Expired

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