US3827973A - Reforming with a coprecipitated platinum-lead catalyst - Google Patents

Reforming with a coprecipitated platinum-lead catalyst Download PDF

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Publication number
US3827973A
US3827973A US00200071A US20007171A US3827973A US 3827973 A US3827973 A US 3827973A US 00200071 A US00200071 A US 00200071A US 20007171 A US20007171 A US 20007171A US 3827973 A US3827973 A US 3827973A
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United States
Prior art keywords
catalyst
platinum
lead
percent
hydrocarbon
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Expired - Lifetime
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US00200071A
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English (en)
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N Kominami
T Iwaisako
K Ohki
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
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    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C07C5/415—Catalytic processes with metals
    • C07C5/417—Catalytic processes with metals of the platinum group
    • 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

Definitions

  • the present invention derived from the discovery, is concerned with a method of producing aromatic hydrocarbons which comprises treating a hydrocarbon or a hydrocarbon mixture at a temperature from 300 C. to 650 C.
  • a catalyst comprising platinum and lead or a catalyst comprising platinum, lead and at least a member selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, germanium, bismuth, chromium, molybdenum, tungsten, uranium, rhenium, ruthenium, rhodium, palladium, osmium and iridium.
  • the catalyst is prepared by a coprecipitation method.
  • benzene, toluene, xylenes and polymethylbenzones are produced by quite simple procedures at low cost because of high concentration and yield of aromatics in the reformate produced according to this invention.
  • a distillate of higher boiling point than toluene or xylene in the reaction product contains neither parafiin nor naphthene and then separation can be effected by distillation only, without application of solvent extraction.
  • Such a distinction from the prior processes is ascribed to high activity and selectivity of the catalyst of this invention in terms of aromatic formation, namely dehydrogenation or dehydrocyclization reactions.
  • life of the catalyst of this invention is so long that frequency in regeneration of the catalyst is reduced under normal reaction conditions in industrial operation.
  • the catalyst of this invention is operative at lower pressures than in the prior processes.
  • the rate of degradation in activity in the prior catalysts is much more drastic and they become inoperative during long operation, and, therefore, the process on an industrial scale has to be carried out under high pressures.
  • the catalyst of this invention is stable in the course of a long operation to give a high yield of aromatics.
  • platinum component of the catalyst there may be used, for example, the hydroxide, platinum halides, chloroplatinic acid or hydrate or ammonium salt thereof. Especially preferred are substances containing a halogen.
  • the halogen and especially chlorine present in the compound advantageously contribute to the catalytic activity like in other platinum reforming catalysts.
  • the preferable amount of chlorine contained in the catalyst of the present invention is in the range of 0.1- 2.0% by weight and particularly in the range of (LS-4.5% by weight based on the total weight of catalyst components.
  • the lead component there may be employed halogenides, inorganic and organic salts, hydroxide, oxide and the like.
  • the element used as the third component may be in the form of its oxide, hydroxide, halide or other inorganic and organic salt or complex.
  • the platinum, lead and the third components may be in the form of a salt containing each of them.
  • Contents of the platinum, lead and the third components are 0.01% by weight, 0.01-5 by weight and 0-3% by weight, respectively, and preferably 0.1-1% by weight, (Ll-3% by weight and 01% by weight, respectively based on the total weight of catalyst components, with the ratio of lead to platinum ranging from 0.1 to 7 and preferably from 0.3 to 3.0.
  • the ooprecipitation method refers to a method wherein a solution of carrier compo nent and catalyst components are mixed and all of the components either form a gel or are precipitated.
  • a catalyst is obtained by adding a catalyst active component to an aqueous solution or sol of a carrier component such as, e.g., alumina, silica and silica-alumina, and removing solvent by vaporizing to dryness or spray drying.
  • a pH adjusting agent such as, e.g. aqueous ammonia, may be added to the solution or sol to effect gelation in a short period of time, followed by drying.
  • a catalyst active component is dissolved in an aqueous solution of a compound which may be converted into a solid carrier such as, e.g., aluminum chloride, or an aqueous solution of a catalyst active component is-added to an aqueous -solution of the carrier component.
  • a neutralizing agent such as, e.g., aqueous ammonia, is added to precipitate both said components followed by drying to obtain a catalyst.
  • amounts of platinum, lead and a third component contained in the aqueous solution of platinum compound, lead compound and a third component are generally 0.01- 5 wt. percent Pt, 0.01-5 wt. percent Pb..and.0-3 wt. percent third component, preferablyltllel wt. percent Pt,
  • Ratio of Pt to Pb in the solution ranges 0.1 57.0, preferably 0,3-3.0. As with the conventional'catalysts,
  • a carrier such as silica alumina, alumina, alumina hydrate, silica, zeolite, kaolin, acid clay or bentonite is.
  • effective and preferable carriers are alumina, silica alumina, zeoliteand the like.
  • hydrocarbons which may be used in the present invention as the starting material-in include those mainly comprising parafiins, olefins ,and naphthen e. having .a boiling point within the range of from, 40 to 350 C., which may be used alone or in admixture of two or more kinds.
  • Preferable hydrocarbons are those having from 6 to 12 carbon atoms
  • Most advantageous materialsfromthe industrial standpoint are naphthas having a boiling range of 40 l90 C., kerosene having a boiling range of 160-260 C., andgas oil having a boiling range of 220-350 C.
  • Feeding ratio of hydrogen to hydrocarbon in gas vol ume is from 0.5 to 15 and preferably from 2 to '10.
  • Feeding rate of the hydrocarbon in terms of LHSV which stands for liquid hourly space velocity (the feeding amount of hydrocarbon per unit time, per unit volume of catalyst, in ml.) is from 0.2 to 10 hr.- and preferably from 0.5 to 5 hr.”
  • reaction pressure is dependent upon the desired quality of product and economy and may be optionally chosen within the range of from 1 to 50 kg./cm. and preferably from 5 to 20 kg./cm.
  • the reaction is preferably carried out under an elevated pressure.
  • gaseous mixture of hydrogen and kerosene having a composition shown below in a feed ratio of 4:1 was continuously passed through the catalyst layer maintained at 510 Cjat an LHSV of 2.0 hr.- under a reaction pressure of 4 kg./cm. (gauge) for 15 hours.
  • the catalyst was prepared by the following procedure.
  • alumina sol (10 wt. percent assay) were added 100 cc. of a mixed aqueous solution containing chloroplatinic acid in a concentration of 0.0256 mol./ liter and lead nitrate in a concentration of 0.169 moL/liter and heated on an oil bathwith stirring to vaporize-to dryness.
  • the resulting mass on which both of said components were supported was'calcined at 550 C. for 5 hours to obtain a catalyst having a composition of 0.5 wt. percent Pt, 3.5 wt. percent Pb and A1 Composition of the starting kerosene (vol percent):
  • Example 3 To 1000 g. of alumina sol (10 wt. percent assay) were added 100 cc. of a mixed aqueous solution containing chloroplatinic acid in a concentration of 0.0256 mol./ liter and lead nitrate in concentrations specified in the following Table. The resulting mixture was heated on a hot bath with stirring to vaporize it to dryness. The resulting mass on which both of said components were supported was calcined at 550 C. for 5 hours.
  • the resulting catalysts had compositions of: 0.5 wt. percent Pt, 0.152.5 wt. percent'Pb and A1 0 while Pb/Pt ratio ranged from 0.3 to- 5.0.
  • Method of producing aromatic hydrocarbons which comprises hydroforming a mixture of hydrogen and a hydrocarbon over a catalyst at a temperature of from 300 C. to 650 C. under a pressure of from 5 to 20 kg./cm.
  • said catalyst consisting essentially of from about 0.01 to about 5 weight percent of platinum and from about 0.01 to about 5 weight percent of lead, up to about 1% by weight of a component selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, germanium, bismuth, chromium, molybdenum, tungsten, uranium, rhenium, ruthenium, rhodium, palladium, osmium and iridium, up to 2.0% by weight of a halogen and a carrier, wherein the ratio of lead to platinum is from 0.1 to 7, and being prepared by coprecipitating said platinum and lead components upon a carrier.
  • Method of producing aromatic hydrocarbons which comprises hydroforming a mixture of hydrogen and a hydrocarbon over a catalyst at a temperature of from 300' C. to 650 C. under a pressure of from 5 to 20 kg./ cm, said catalyst consisting essentially of from about 0.01 to about 5 weight percent of platinum and from about 0.01 to about 5 weight percent of lead and a carrier, wherein the ratio of lead to platinum is from 0.1 to 7, and being prepared by coprecipitating said platinum and lead components upon a carrier,

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00200071A 1969-02-10 1971-11-18 Reforming with a coprecipitated platinum-lead catalyst Expired - Lifetime US3827973A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP948869 1969-02-10
JP6761769 1969-08-28
JP10381769 1969-12-25

Publications (1)

Publication Number Publication Date
US3827973A true US3827973A (en) 1974-08-06

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ID=27278502

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US00200071A Expired - Lifetime US3827973A (en) 1969-02-10 1971-11-18 Reforming with a coprecipitated platinum-lead catalyst
US00200065A Expired - Lifetime US3827988A (en) 1969-02-10 1971-11-18 Pt-pb catalyst compositions
US00200064A Expired - Lifetime US3827972A (en) 1969-02-10 1971-11-18 Method of producing aromatic hydrocarbons

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US00200065A Expired - Lifetime US3827988A (en) 1969-02-10 1971-11-18 Pt-pb catalyst compositions
US00200064A Expired - Lifetime US3827972A (en) 1969-02-10 1971-11-18 Method of producing aromatic hydrocarbons

Country Status (4)

Country Link
US (3) US3827973A (enrdf_load_stackoverflow)
DE (1) DE2005828C3 (enrdf_load_stackoverflow)
GB (1) GB1305137A (enrdf_load_stackoverflow)
NL (1) NL162353C (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900387A (en) * 1972-03-10 1975-08-19 Universal Oil Prod Co Hydrocarbon conversion with a multimetallic catalytic composite
US3928177A (en) * 1972-01-10 1975-12-23 Universal Oil Prod Co Hydrocarbon conversion with a multimetallic catalytic composite
US4072602A (en) * 1972-01-10 1978-02-07 Uop Inc. Dehydrogenation method and nonacidic multimetallic catalytic composite for use therein
CN112742382A (zh) * 2019-10-29 2021-05-04 中国石油化工股份有限公司 一种催化重整催化剂的制备方法

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1390182A (en) * 1971-03-16 1975-04-09 Johnson Matthey Co Ltd Catalysis
JPS51963B1 (enrdf_load_stackoverflow) * 1971-07-05 1976-01-13
US3915846A (en) * 1973-04-23 1975-10-28 Universal Oil Prod Co Hydrocarbon conversion with a trimetallic catalytic composite
US3980726A (en) * 1973-06-01 1976-09-14 Universal Oil Products Company Dehydrogenation with a nonacidic multimetallic catalyst
US3940329A (en) * 1974-01-24 1976-02-24 Universal Oil Products Company Hydrocarbon conversion with a multimetallic catalytic composite
US4053389A (en) * 1974-06-13 1977-10-11 Uop Inc. Hydrocarbon conversion with an acidic multi-metallic catalytic composite
US4028225A (en) * 1974-06-13 1977-06-07 Uop Inc. Hydrocarbon conversion with a sulfided acidic multimetallic catalytic composite
US4130597A (en) * 1975-07-21 1978-12-19 Wilhelm Frederick C Dehydrogenation using multimetallic catalyst
DE3306907A1 (de) * 1983-02-26 1984-08-30 Basf Ag, 6700 Ludwigshafen Katalysator und seine verwendung zur herstellung von methylmethacrylat
US4899012A (en) * 1988-10-17 1990-02-06 Uop Catalyst for the isomerization of aromatics
FR2666249B1 (fr) * 1990-09-03 1994-07-22 Inst Francais Du Petrole Catalyseur et procede d'aromatisation des hydrocarbures contenant 2 a 4 atomes de carbone par molecule.
US5268522A (en) * 1990-09-03 1993-12-07 Institut Francais De Petrole Process for the aromatization of hydrocarbons containing 5 to 9 carbon atoms per molecule in the presence of a particular catalyst
FR2674769B1 (fr) * 1991-04-04 1994-04-29 Inst Francais Du Petrole Catalyseur du type galloaluminosilicate contenant du gallium, un metal noble de la famille du platine et au moins un metal additionnel, et son utilisation en aromatisation des hydrocarbures.
FR2840548B1 (fr) * 2002-06-07 2005-03-18 Inst Francais Du Petrole Lit homogene de catalyseur et procede de transformation d'hydrocarbures en composes aromatiques avec ledit lit
US9242233B2 (en) 2012-05-02 2016-01-26 Saudi Basic Industries Corporation Catalyst for light naphtha aromatization
US9180441B2 (en) 2012-09-20 2015-11-10 Saudi Basic Industries Corporation Method of forming zeolite shaped body with silica binder
US9782758B2 (en) 2013-04-23 2017-10-10 Saudi Basic Industries Corporation Method of preparing hydrocarbon aromatization catalyst, the catalyst, and the use of the catalyst

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928177A (en) * 1972-01-10 1975-12-23 Universal Oil Prod Co Hydrocarbon conversion with a multimetallic catalytic composite
US4072602A (en) * 1972-01-10 1978-02-07 Uop Inc. Dehydrogenation method and nonacidic multimetallic catalytic composite for use therein
US3900387A (en) * 1972-03-10 1975-08-19 Universal Oil Prod Co Hydrocarbon conversion with a multimetallic catalytic composite
CN112742382A (zh) * 2019-10-29 2021-05-04 中国石油化工股份有限公司 一种催化重整催化剂的制备方法
CN112742382B (zh) * 2019-10-29 2024-01-05 中国石油化工股份有限公司 一种催化重整催化剂的制备方法

Also Published As

Publication number Publication date
NL162353B (nl) 1979-12-17
NL7001852A (enrdf_load_stackoverflow) 1970-08-12
US3827972A (en) 1974-08-06
US3827988A (en) 1974-08-06
GB1305137A (enrdf_load_stackoverflow) 1973-01-31
DE2005828B2 (de) 1973-08-09
DE2005828A1 (de) 1970-09-03
NL162353C (nl) 1980-05-16
DE2005828C3 (de) 1974-03-07

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