US3607969A - Process for hydrogenating unsaturated compounds in c3-hydrocarbon fractions - Google Patents

Process for hydrogenating unsaturated compounds in c3-hydrocarbon fractions Download PDF

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Publication number
US3607969A
US3607969A US858548*A US3607969DA US3607969A US 3607969 A US3607969 A US 3607969A US 3607969D A US3607969D A US 3607969DA US 3607969 A US3607969 A US 3607969A
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United States
Prior art keywords
percent
hydrogenation
catalyst
hydrogen
unsaturated compounds
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Expired - Lifetime
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US858548*A
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English (en)
Inventor
Walter Kronig
Wilhelm Mayrhofer
Gerhard Scharfe
Kurt Halcour
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Bayer AG
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Bayer AG
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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
    • 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
    • B01J23/44—Palladium
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble 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
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium

Definitions

  • This invention relates to a process for hydrogenating unsaturated compounds in c -hydrocarbon fractions.
  • hydrocarbon fractions with three carbon atoms in the molecule are obtained, these fractions containing varying quantities of unsaturated compounds, mainly propylene, but possibly also more strongly unsaturated compounds.
  • the content of propylene in these C -fractions is generally between 35 percent and 95 percent by volume. If the conversion of the hydrocarbons being used is carried out at relatively high temperatures, especially above 600 C. but in particular between 700 and 900 C., the C -fractions which are formed also contain methyl acetylene and propadiene in quantities between 0.1 percent and percent in addition to propylene and propane.
  • the C -fractions obtained in the conversion processes are now not suitable for direct use for all purposes.
  • liquid hydrocarbons are subjected to pyrolysis besides the primarily desired ethylene also other unsaturated hydrocarbons, such as propylene, are always obtained.
  • the ratio of the consumption of ethylene and propylene often does not correspond to the ratio of the formation of these two hydrocarbons in the pyrolysis, since the need for propylene is not equal to the quantity formed. Consequently, it is frequently desirable to use this C -fraction for the pyrolysis in order to produce ethylene therefrom.
  • the starting materials used for the new process should consist substantially of C -hydrocarbons containing substantial quantities of propane, e.g. 30 to 95 percent.
  • Other constituents which may be contained therein are, for example, propane and other unsaturated hydrocarbons such as methyl acetylene and propadiene. However, they may also contain fractions of lower or higher hydrocarbons, e.g. C or C hydrocarbons. it is desirable for the starting materials to be as far as possible free from hydrogen sulfide and carbon oxysulfide.
  • a part of the hydrogenation product is returned to the inlet of the reaction chamber.
  • This return is preferably ef fected without relaxation. of the pressure of the returned material, for example, from a separator which is connected after the reactor and in which the hydrogenation product is collected and separated from the gases.
  • the quantity of returned product is chosen to be between 0.3 and three parts by weight of returned product for each part by weight of fresh product and advantageously one to two parts by weight for each part by weight of fresh product. In certain cases, it is desirable slightly to lower the temperature of the returned product before the introduction thereof into the inlet of the reactor.
  • the throughput of fresh material through the reactor can generally be, for example, between 2 and 20 kg.
  • the hydrogen gas to be introduced should contain at least 50 percent of hydrogen. Hydrogen contents higher than percent are advantageous.
  • the hydrogen gas should be as free as possible from carbon monoxide and also from hydrogen sultide and carbon oxysulfide.
  • the quantity of hydrogen to be introduced into the reaction is measured in such a way that there is generally available an excess of 10 percent or more of hydrogen as compared with the calculated consumption for the hydrogenation of all unsaturated compounds. In general, it is not necessary for the excess of introduced hydrogen to be raised to more than 50 percent. On account of this small hydrogen excess, it is not necessary for the hydrogen gas to be recycled.
  • the process according to the invention is preferably carried out at temperatures between 10 C. and C. and advantageously from 20 C. to 50 C., it having proved desirable to allow the temperature to rise slightly during the flow through the reaction chamber, for example by [0 C. to 30 C. (from the inlet to the outlet of the reactor).
  • the pressures to be used are advantageously controlled in such a way that they are sufficiently higher than the saturation pressure of the initial material being used at the temperature chosen.
  • the hydrogen partial pressure should be at least 10 percent of the hydrocarbon partial pressure at the highest hydrogenation temperature employed. It is generally sufficient to have a hydrogen partial pressure which is not higher than the hydrocarbon partial pressure. Total pressures from 10 to 50 atm. gauge are suitable.
  • Noble metals in the VIIlth group of the Periodic System of the elements are suitable as catalysts for carrying out the process. These metals are used in quantities of about 0.05 percent to 2 percent and advantageously 0.1 percent to 1 percent on a support.
  • Aluminum oxide which may also contain relatively small quantities of other oxides, such as silicon dioxide, is for example suitable as a support.
  • the aluminum oxides may have intrinsic surfaces between 5 and 300 m. /g.
  • Aluminum oxide supports with surfaces of less than mF/g. are advantageously used. Supports which consist wholly or partially of aluminum spinel are also particularly suitable. Lithium, beryllium, magnesium, copper, manganese and nickel are of particular value as spinel-fonning metals.
  • the proportion of spinel in the support is advantageously at least 20 percent by weight but as far as possible 40 percent or higher.
  • Supports which have proved especially suitable are those in which the sup ort consists almost completely, for example, of 95 percent to 100 percent, of spinel.
  • the spinels are desirably produced from highly active aluminum oxide with an intrinsic surface of from about 200 to 300 mF/g. which is transformed into spinels by reaction with the compounds of the spinel-forming metals.
  • the aluminum oxide in lump form (small cylinders, pellets or balls), to saturate it with the solution of a compound (salts or hydroxides) of the spinel-forming metal which is to be used and to produce the spinel formation, optionally after intermediate thermal decomposition of the salt, by heating for l to hours at 900 C. to l,300 C.
  • a compound salts or hydroxides
  • the catalyst support was constituted by a heat-treated aluminum oxide in small cylinder form with an intrinsic surface of 12 m. /g., to which 0.5 percent of palladium metal had been applied by saturating the cylinders with sodium-palladium chloride and precipitating the palladium with hydrazine hydrate.
  • This catalyst was introduced into a vertically disposed tube having an internal diameter of 20 mm. and a length of 1,500 mm.
  • a C -fraction was introduced, which had been obtained by separation of gases from the pyrolysis of light naptha.
  • the C -fraction had the following composition:
  • EXAMPLE 3 A 'y-Al o in spherical form was saturated with an aqueous nickel acetate solution and heat-treated for 10 hours at l,000 C. X-ray analysis of this support showed: 85% of (X-A12O3 +10% of nickel-aluminium spinel +5% of a nickel-0x0 compound.
  • the support was saturated with an aqueous sodium-palladium chloride solution and washed and the palladium was then reduced.
  • the prepared catalyst contained 0.6 percent by weight of Pd and 6.0 percent by weight of M0, the remainder being A1 0 Using the catalyst prepared in this way, hydrogenation was carried out with the CK -fraction indicated below.
  • the apparatus mentioned in example 1 was used and the hydrogenation conditions were as indicated below. The conditions and the results of the hydrogenation are apparent from the following data.
  • the reaction temperature was 40 C. at the inlet to the reactor and C. at the end of the catalyst bed.
  • the hydrogen input was regulated in such a way that 20 percent more hydrogen was introduced and correspondingly released at the end of the reactor than corresponded to the chemical consumption. From the hydrogenation product collected in the connected separator, twice the quantity, related to the fresh product introduced, was returned to the inlet of the reactor without release of pressure The fresh input was 7 kg. per liter of catalyst per hour.
  • the hydrogenation product removed from the system had the following composition:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US858548*A 1965-05-08 1969-04-11 Process for hydrogenating unsaturated compounds in c3-hydrocarbon fractions Expired - Lifetime US3607969A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEF0046004 1965-05-08
US85854869A 1969-04-11 1969-04-11

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US (1) US3607969A (enrdf_load_stackoverflow)
NL (1) NL6606236A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5059732A (en) * 1988-03-23 1991-10-22 Institut Francais Du Petrol Process for selective catalytic hydrogenation in liquid phase of a normally gaseous feed containing ethylene, acetylene and gasoline

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5059732A (en) * 1988-03-23 1991-10-22 Institut Francais Du Petrol Process for selective catalytic hydrogenation in liquid phase of a normally gaseous feed containing ethylene, acetylene and gasoline

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Publication number Publication date
NL6606236A (enrdf_load_stackoverflow) 1966-11-10

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