Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
  • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
  • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
  • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
  • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
  • C01B2203/1052—Nickel or cobalt catalysts

Definitions

• This. invention relates to the catalytic decomposition of'hydrocarbons and more particularly to such a processutilizing hydrocarbons containing sulfur in amounts. greater than O .5grain per 100 cu. ft. of vaporized hydrocarbon.
• a. gaseous mixture of. steam and substantially sulfur-free hydrocarbon is. passed over a heated catalytic agent containing nickel.
• the process is carried out in' a furnace fired through the arch, with flue. gases withdrawn from the base of the furnace and; with the steam-hydrocarbon mixtureipassing through the" catalyst tubes parallel to and concurrent: with the flow of heat media.
• the cracked gases are then passed through a secondary furnace and air introduced in order to obtain anoptimum. temperature to reduce the methane content of the: exit gaseslt'o a'valuebelow 1%.
• the CH4 content can; be 0.1% or less if desired.
• Steamgas ratios less than Z may beutilized when using natural. gas as the. hydrocarbonv and are. not limited as in the first procedure. described-
• the cracking efficiency, or per cent cracking obtained is controlled by the steam gas ratio, the spacevelocity, the catalyst quality and the reaction temperature.
• the pen ent Having selected'a suitable steamgas ratio, space velocity and catalyst, in accordance withiprinciples: well known in the art, the pen ent; crackinggisi obtained. by a suitable adjustment of the. temperature; within the: limita t ions' of'the particular process; In practice such processes are'condu'cted' at temperatures just sufficient to yield the desired conversion, or cracking efficiency, based upon raw materials com-F.
• High cracking efiiciencies are obtained by this improvement, which have heretofore been regarded as impossible, and from a range of sulfur-containing hydrocarbons, from those moderate in sulfur content, such as propane, to those heavy in sulfur content, such as crude oils.
• a catalyst comprising 25% nickel, 25% zirconium silicate, and 50% magnesia by weight was made up in the form of pellets and placed in the cracking tube of a hydrogen furnace.
• a sulfur-free hydrocarbon and steam were then passed through the cracking tube under conditions and with results set forth in column 1, Table I, below.
• a petroleum oil containing 1% sulfur was then atomized, vaporized, mixed with steam and passed through the cracking tube under the same conditions of steam-gas ratio, space velocity, catalyst quality and temperature.
• the per cent cracking or cracking efiiciency fell off to as shown in column 2, Table I.
• the temperature was then increased C.'and the crackin efficiency rose to 98% as shown in column 3, Table I.
• EXAMPLE 2 A catalyst comprising 10% nickel, 10% aluminum oxide, and 80% magnesia by weight was made up and the same procedure followed as in Example 1. Conditions of treatment and results are shown in Table II below.
• the sulfur-free hydrocarbon gave a cracking efficiency of 99% as shown in column 1.
• the petroleum oil (same as used in Example 1) containing 100 grains of sulfur per 100 cu. ft. of vaporized hydrocarbon, gave a cracking efficiency of 88% under the same conditions of steam-carbon ratio, space velocity, catalyst quality, and temperature, as shown in column 2. Raising the temperature from 800 C. to 900 C. increased the cracking efficiency from 88% to 98% as shown in column 3. A further increase in temperature to 950 C. gave a cracking efficiency of 99%.
• LA catalyst comprising nickel, 40% zirconium silicate and 50% magnesia by weight was made up .and the'sameprocedure followed as in Example .1. Conditions or treatment and results are shown in'Table III below.
• Thesulfur-iree hydrocarbon gave. a cracking. efficiency of 97-98% as shown in column'l.
• the 'petroleum'oil utilized in Example 1 and containing 100 grains of sulfur per'100 cu. ft. of vaporized hydrocarbon gave a reduced cracking efilciency of 88% as shownin co1umn2. However; when the temperature was increasedto 900 C.
• a nickel catalyst containing more than 10% nickel by weight Suitable catalysts of this type are nickel-zirconium silicate-magnesia, nickelaluminum oxide-magnesia, nickel-zirconium silicate, nickel-aluminum oxide, nickel-diaspora, nickel-magnesia, nickel-pumice, nickel-titanium oxide, etc. These catalysts may be made by any of the methods of the prior art and are desirably given a preliminary tempering treatment with heat prior to use.
• sulfurcontaining hydrocarbon is defined as a hydrocarbon containing more than 0.5 grain of sulfur per 100 cu. ft. of vaporized hydrocarbon treated; optimum temperature is defined as the lowest temperature required in practice to obtain a given per cent of cracking with a'given steam-carbon ratio, space velocity and catalyst quality; crack.- i'ng efficiency is defined as per cent conversion of the carbon in the hydrocarbon to CO; steamcarbon ratio is defined as the ratio of the mols of steam to the mols of carbon in the hydrocarbon being treated; thus in the case of propane a ratio of 2:1 would mean 6 volumes of steam for each volume of propane; space velocity is defined as the volume of steam-hydrocarbon mixture per volume of catalyst per hour; catalyst quality is defined as the activity of the catalyst under a given set of conditions, i. e., type and age of catalyst and conditions of use.
• the process of the present invention is particularly useful in the manufacture of hydrogen by the catalytic decomposition of hydrocarbons.
• the invention is not, however, limited to hydrogen 'prod uction but is applicable, as well, to
• a one step process for catalytic cracking of sulfur polluted fluid hydrocarbons to produce high Weight yields of hydrogen and carbon oxides which comprises passing a mixture of steam and a fluid hydrocarbon containing at least 1 gr. of suliurper 100 cu. ft. of hydrocarbon in gaseous phase over a heated catalytic body containing at least 10% nickel, at least part of the catalytic body being maintained at a temperature of at least 900 C.
• a one step process for catalytic cracking of sulfur polluted fluid hydrocarbons to produce high weight yields of hydrogen and carbon oxides which comprises passing a mixture of steam and a fluid hydrocarbon containing at least 1 gr. of sulfur per 100 cu. ft.
• a one step process for catalytic cracking of sulfur polluted fluid hydrocarbons to produce high weight yields of hydrogen and carbon oxides which comprises passing a mixture of steam and a normally liquid petroleum hydrocarbon containing at least gr. of sulfur per 100 cu. ft. of vaporized hydrocarbon over an externally heated catalytic body containing at least 10% nickel, at least part of the catalytic body being maintained at a temperature of at least 900 C.
• a one step process for catalytic cracking of sulfur polluted fluid hydrocarbons to produce high weight yields of hydrogen and carbon oxides which comprises passing a mixture of steam and a normally liquid petroleum hydrocarbon containing at least 100 gr. of sulfur per 100 cu. ft. of vaporized hydrocarbon over an externally heated catalytic body containing at least 10% nickel at a space velocity of at least 300 volumes per hour per volume of catalyst, at least part of the catalytic body being maintained at a temperature of 900 C., and said mixture of steam and hydrocarbon having a steam to carbon ratio of about 2 to about 4.5

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Inorganic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

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Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

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Cited By (9)

Citations (8)

• 1946
  • 1946-06-20 US US678163A patent/US2628890A/en not_active Expired - Lifetime
• 1947
  • 1947-06-03 GB GB14695/47A patent/GB640368A/en not_active Expired
  • 1947-06-06 FR FR947572D patent/FR947572A/fr not_active Expired

Patent Citations (8)

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