US3689401A - Process for treating by-product heavy fractions formed in the production of olefins - Google Patents

Process for treating by-product heavy fractions formed in the production of olefins Download PDF

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US3689401A
US3689401A US97231A US3689401DA US3689401A US 3689401 A US3689401 A US 3689401A US 97231 A US97231 A US 97231A US 3689401D A US3689401D A US 3689401DA US 3689401 A US3689401 A US 3689401A
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oil
catalyst
temperature
nickel
product
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Shinpei Gomi
Masaaki Takahashi
Tadashi Ishiguro
Akio Okagami
Kunihiko Uemoto
Hiroshi Kuribayashi
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Kureha Corp
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Priority claimed from JP45011341A external-priority patent/JPS5011377B1/ja
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • 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
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation

Definitions

  • ATTORNEYS United 'States Patent 01 has 3,689,401 Patented Sept. 5, 1972 PROCESS FOR TREATING BY-PRODUCT HEAVY FRACTIONS FORMED IN THE PRODUCTION OF OLEFINS Shinpei Gomi, Masaaki Takahashi, Tadashi Ishiguro, and Akio Okagami, Tokyo, and Kunihiko Uemoto and Hiroshi Kuribayashi, Kanagawa, Japan, assignors to Kureha Kagaku Kogyo Kabushiki Kaisha, Tokyo,
  • the present invention relates to a process for the treatment of heavy oil fractions formed as by-products in the production of olefins.
  • An object of the process of this invention is the treatment of the by-product heavy fractions by the application thereto of a sequence of a plurality of process steps involving a hydrogenating step in which the polycondensed aromatic hydrocarbon compounds in the feed stock are mainly hydrogenated without any change in their ring structures.
  • this hydrogenating step it is already known in the art to use sulfides of tungsten and molybdenum as the catalyst for the nuclear hydrogenation.
  • reaction of olefins with hydrocarbons the reaction of a pure aromatic hydrocarbon with an olefin, known as an alkylation process, for example, the alkylation of benzene with ethylene in the presence of anhydrous aluminum chloride and like catalysts produces ethyl benzene and also naphthalene is converted to aand fi-naphthalenes (U.S. Pat. 2,515,237, U.S. Pat. 2,570,263, Japanese patent publication No. 7,731/38).
  • the process of this invention comprises a process for the treatment of by-product heavy fraction formed in the production of olefins in which the by-product heavy fractions formed in the production of gaseous olefins by the thermal cracking of hydrocarbons are thermally stabilized in a first step by a treatment using a specific catalyst having superior selectivity, then the resulting heavy fractions are treated using a hydrorefining step, thereafter the prodnet is treated by reacting with olefin and/or by hydrogenation in a subsequent step to thereby obtain improved hydrocarbon oil products having excellent anti-freezing properties, thermal stability, oxidation stability at elecated temperature, solubility, electric properties and a good color appearance.
  • the present invention is a process for the treatment of by-product heavy fractions formed in the production of olefins. More particularly, the present invention is a process for the treatment of the by-product heavy fractions which are obtained upon the thermal cracking of such hydrocarbons as crude oil, asphat, heavy oil, kerosene, naph tha and liquefied petroleum gas at a temperature above 700 C. to produce acetylene and gaseous olefins, such as ethylene and propylene, in which the by-product heavy fractions have an initial boiling point of above 160 C. and have a 75% distill-off point of below 450 C.
  • the above-described by-product heavy fractions used as the raw feed stock are firstly treated with hydrogen under reaction conditions of a temperature of from 40 to 200 C., a pressure of from to 300 l g./cm. G, and a liquid residence time of from 0.1 to 2.0 hours using a nickel-containing catalyst which has been reduced to the metallic state followed bya treatment with organic sulfur compounds consisting exclusively of carbon, hydrogen and sulfur atoms, to thereby impart to the by-product heavy fractions thermal stability; then the resulting stabilized oils are subjected to hydrorefining at a temperature of from 250 to 450 C., a pressure of from 5 to 300 kg./cm.
  • the by-product heavy fractions to be treated according to the process of this invention are obtained by the thermal cracking of hydrocarbons at a temperature above 700 C.
  • the by-product heavy fractions are rearranged so as to contain predominantly an aromatic-rich fraction, and can be utilized quite advantageously depending upon the method of their treatment.
  • they contain a fairly large proportion of thermally unstable substances which are readily converted into resinous materials upon heating to cause deposition on the walls of the equipment, such as heat exchangers, and on the catalyst surface.
  • the by-product heavy fractions to be treated according to the process of this invention not only include normally liquid oils but also include those existing as solids at normal temperatures.
  • Embodiments of the process of this invention comprise mainly treatments including a step in which thermal stability is imparted to the product heavy fractions and a hydrorefining step, and further treatments in the step of reaction with an olefin and/or the step of hydrogenation.
  • hydrocarbon oil having better properties and more advantageous performance characteristics than that of untreated by-product heavy fractions, i.e., a considerably lower pour-point, a higher viscosity index as well as improved thermal stability, electric properties, color appearance and solubility.
  • the product hydrocarbon oil thus obtained exhibits superior properties which are especially suited for use as lubricating oils, heat transfer media, electrical insulating oils (condenser oils, ultrahigh voltage cable oils, high voltage transformer oils), paint vehicles, solvents, plasticizers, rubber process ing oils, jet engine fuels, and the like.
  • the process of the present invention in particular concerns treatment of the byproduct heavy fractions formed upon the production of olefins whereby a hydrocarbon oil having superior performances can be obtained by the treatment in a sequence of characteristic procedures of the by-product heavy fractions, which have been scarcely utilized efficiently due to particularly complicated properties of the components contained therein.
  • the present invention has now found great industrial significance in the efficient utilization of by-product heavy fractions which are produced in increasing quantity especially due the increasing capacity of ethylene production as well as the shifting trend towards heavier feed stocks for cracking feeds.
  • the feed material is pumped to line 1 under a pressure of from 5 to 300 kg./cm. G and heated after being mixed with compressed hydrogen from 2, at from 40 to C. using preheater 3 and heat exchanger 4.
  • a reactor 5 is provided as to as impart thermal stability and packed with a nickel-containing catalyst which has been previously treated in a specific manner.
  • the process of the present invention is not only characterized in the treatment of the heavy fraction material by the use of a specifically pretreated nickel catalyst but also in the method for the preparation of aforesaid nickel catalyst.
  • the pretreated catalyst is prepared by contacting a solid catalyst containing at least 1% by Weight (preferably not less than 5% by weight) of nickel in its reduced form at a temperature below 150 C, in the presence or absence of hydrogen, with an organic sulfur compound consisting exclusively of carbon, hydrogen and sulfur atoms, such as mercaptans, for example, propyl mercaptan, phenyl mercaptan and benzyl mercaptan; sulfides, for example, dimethyl sulfide and dibutyl sulfide; disulfides, for example, dibenzyl disulfide, polysulfides and thiophene, either directly or, if desired, as a diluted mixture with hydrocarbons, in the gaseous or liquid phase in a ratio of at least 0.01 sulfur atom per nickel atom. Then the catalyst is allowed to stand for a period of not less than 10 seconds.
  • feed stock itself for the pretreatment of the solid catalyst containing the nickel in the reduced state, since the feed material contains at least one of such organic sulfur-containing compounds as described previously.
  • the total amount of copper and chromium is preferably not greater than 10% by weight based on the nickel in the catalyst, and the ratio of copper to chromium is preferably about 1:1.
  • Nickel catalyst can be used instead of the nickel catalyst, but the use of the nickel catalyst is more advantageous since it is much more resistant to deactivation even in the presence of carbon monoxide and small amounts of hydrogen sulfide, and it is less expensive than palladium.
  • the nickel catalyst pretreated with the organic sulfur compounds in this reaction step By using the nickel catalyst pretreated with the organic sulfur compounds in this reaction step, it is now possible to avoid any saturation of non-conjugated olefins as well as to avoid hydrogenation of the aromatics. It is also to prevent the reaction from going out of control due to an excessive increase in the reaction temperature arising from exothermic heat resulting in various hydrogenation reactions of the hydrocarbons, particularly hydrogenolysis, which leads to considerable loss of the useful components in the feed stock. Thus, the reaction takes place smoothly under milder temperature conditions unaccompanied by polymerization of the thermally unstable components to thereby keep the preheater and catalyst clean over an extended period of time. This has never been attained using conventional nickel sulfide catalysts which necessarily must be operated at temperatures as high as 200 C. or above due to their lower catalytic activity.
  • the reaction conditions to be employed in this step involve a temperature of from 40 to 200 C., a pressure of from S to 300 kg./cm. G and a liquid residence time of from
  • Hydrorefining step The oil which has been stabilized in the preceding step is heated in furnace 6 and treated in hydrorefining reactor 7 wherein desulfurization and denitrogenation are accomplished simultaneously. Sulfur compounds poison the nickel-containing catalyst used in the later hydrogenation step, described hereinafter, and basic nitrogen-containing compounds poison the catalyst used in the reaction with olefins. For these reasons, the hydrorefining step is necessary to remove poisonous sulfur-containing and basic nitrogen-containing compounds. This hydrorefining step is carried out at a temperature of from 250 to 450 C., a pressure of from to 300 kg/cm.
  • the composition at the outlet of 7 is determined such that the molar ratio of hydrogen to the oil material is not less than 0.1.
  • the hydrorefined oil withdrawn from the reactor 7 is cooled in 3 and heat exchanged in 8 and separated into the gas and liquid phases in separator 9.
  • the hydrogenrich gas obtained at line is recirculated via line 42 while a portion of the gas is released via line 41 from the system.
  • the refined oil obtained at 9 is heated, if
  • Step for reacting with an olefin The hydrorefined oil thus obtained is then sent to a step for reaction with an olefin by being passed through valves 16, 17 and 18, mixed with an olefin fed from line 19 and heated or cooled at 20 to bring it to the necessary temperature of from 40 to 380 C.
  • the refined oil can be passed through valve 13, and then introduced to fractional distillation 14 so as to recover a desirable fraction which is successively passed to the olefin-reacting step through valves 15 and 18.
  • the refined oil or fractionated oil is then mixed with an olefin supplied from line 19, heated or cooled at 20 to the necessary temperature of from 40 to 380 C., and introduced into a reactor 21 operated under a pressure of from 0 to kg./cm. G, a liquid residence time of from 0.1 to 5.0 hours and an olefin to refined oil molar ratio of from 0.1 to 10 to thereby effect the reaction with the olefin.
  • the mole ratio of the olefin to aromatics can be varied depending upon the types and uses of the products, but usually from 1 to 4 moles on the average are required.
  • the number of moles of the olefin added can be adjusted by controlling the reaction temperature, pressure, residence time, and the ratio of olefin to hydrorefined oil.
  • Typical solid acid catalysts which can be used include, for example, silica-alumina, crystalline aluminosilicate, nickel oxide-silica, silver-oxide silica-alumina, silica-magnesia, alumina-boria and solid phosphoric acid.
  • an additional reactor for example, a second reactor 23 may be connected from the primary reactor 21 after controlling the temperature of the reaction material in cooler 22.
  • a plurality of such as combination of an adiabatic reactor with an inter cooler may be installed if desired.
  • the product which has been reacted with the olefin is then passed to separator 25 from which an excess of olefin obtained at line 26 is recycled to the reactor with or without the release of a portion thereof.
  • separator 25 from which an excess of olefin obtained at line 26 is recycled to the reactor with or without the release of a portion thereof.
  • the degree of gas-liquid separation in this procedure is facilitated by providing cooler 24.
  • reaction product is withdrawn from line 27 and conveyed to, if necessary, a separating section including distillation under reduced pressure and the like, or passed via line 28 to the following hydrogenation step.
  • the olefin to be used can contain impurities such as nitrogen, hydrogen, carbon monoxide, lower saturated hydrocarbons, and the like.
  • the hydrorefined oil to be treated in this step contains in excess of 30 p.p.m. (by weight), as nitrogen, of basic nitrogen-containing compounds
  • a solid acidic substance such as active clay, silica-alumina and solid phosphoric acid
  • the hydrogenation in this step is carried out by reacting at least one of the above pretreated oils with hydrogen at a temperature of from 100 to 400 C., a pressure of from 10 to 300 kg./cm. G and a liquid residence time of from 0.1 to 5.0 hours, using a solid hydrogenating catalyst.
  • a hydrogenating reactor 34 employed in this step is packed with a solid hydrogenating catalyst, one of which consists of Group VI metals of the Periodic Table, such as molybdenum and the like, and Group VIII metals, such as nickel, palladium and platinum, or of a Group VIII metal alone.
  • the solid hydrogenation catalyst to be used in this step can be pretreated according to the following procedure.
  • a nickel-containing catalyst having a nickel content of at least 1% by weight is charged in the hydrogenating reactor 34, then reduced with hydrogen supplied from 31 after being heated at 33 to a temperature of about 150 C. Thereafter, the catalyst is treated under pressure with a sulfur-containing hydrocarbon oil fed from line 32 or with a hydrorefined oil passed via 29 and after being heated at from 180 to 300 C. in 33 in the presence or absence of hydrogen or in the presence of an inert gas to thereby prepare a pretreated nickel-containing catalyst.
  • the pretreatment in the presence of hydrogen is often accompanied by an exothermic hydrogenation reaction, although this is dependent upon the nature of the sulfurcontaining hydrocarbon oil, so that it is necessar'y to control the inlet temperature of the reactor at approximately 180 C.
  • the nickel-containing catalyst having a nickel content of at least 1% by weight used in this step is a powdery or shaped catalyst consisting of nickel and a carrier material of inorganic oxides such as silica, silicaalumina, magnesia and diatomaceous earth. A small amount of copper, chromium, cobalt and the like can be added to the catalyst if desired.
  • the sulfur-containing hydrocarbon oil to be used for the pretreatment of the catalyst has a sulfur content, calculated as sulfur, in the range of from 0.001 to 3.0% by weight, an initial boiling point above 160 C. and is substantially free from hydrogen sulfide, carbon disul-fide, mercaptans, sulfides, disulfides, polysulfides and thiophene.
  • hydrocarbon oils examples include by-product oils from high temperature cracking, hydrorefined heavy cycle oils from fluidized catalytic cracking, kerosene, light oil and the like, which essentially should not contain the above described hydrogen sulfide, carbon disulfide, mercaptans, sulfides, disulfides, polysulfides and thiophene.
  • the hydrorefined oil passed via lines 29 and 30 satisfies the above requirements Well in view of its characteristics and by the fact that it has undergone the hydrorefining treatment.
  • a nickel-containing catalyst pretreated in the manner described hereinabove it is now possible to carry out the nuclear hydrogenation alone selectively due to the stabilized activity of the catalyst.
  • This catalyst has a high activity sufiicient to carry out the nuclear hydrogenation smoothly at a temperature of from 100 to 400 C., a pressure of from 10 to 300 kg./ crn. G. and a liquid residence time of from 0.1 to 5.0 hours.
  • the composition at the outlet of the hydrogenating reactor 34 is controlled in that the molar ratio of hydrogen to the feed oil (being passed through 30) is kept above a value of 0.2.
  • the degree of the nuclear hydrogenation needed for the product will vary depending upon the uses and applications of the product desired, it generally reaches at least When the heat of the reaction becomes too large to carry out the reaction in a single reactor, depending upon the requisite degree of nuclear hydrogenation, it is preferred to provide a second reactor 36 after the reaction mixture has been cooled in an intermediate reactor 35.
  • a second reactor 36 By employing a plurality of combinations of such adiabatic reactors with the intercoolers, it is possible to attain a desired degree of nuclear hydrogenation.
  • the product thus formed is then cooled, if necessary, in a cooler 37, freed from excess hydrogen at 38, and thereafter withdrawn at 40. Hydrogen from 39 is partially released and the remainder is recycled for re-use.
  • the product from 40 can be further separated, if desired, into the desired types of products after distillation under reduced pressure.
  • EXAMPLE 1 A stainless steel reactor having an inner diameter of 100 mm. and a length of 5 mm. was packed with a mixture of aluminum grains of 1 mm. in diameter with catalyst particles of 3 mm. in both diameter and in height and containing by weight of nickel and a small proportion of chromium and copper supported on diatomaceous earth. Purified hydrogen gas was then passed through the reactor at 180 C., under a pressure of 20 atrn. at a flow rate of 5,000 litres (NTP) per hour for a period of 4 hours so as to reduce and activate the catalyst. The hydrogen gas was then replaced by nitrogen while cooling the reactor.
  • NTP 5,000 litres
  • liquid n-heptane containing 2 mole percent of dibutyl sulfide was passed for 20 minutes at a rate of 20 liters per hour under nearly atmospheric pressure while controlling the temperature of the catalyst all over the reactor to within C. :2C.
  • n-heptane was passed at the same rate for an hour to thereby prepare a catalyst to be used in the step for imparting thermal stability.
  • the reaction tube used was externally heated with electric heaters.
  • the oil was then hydrorefined in a reactor containing a sulfurized cobalt-molybdenum catalyst (3 mm. in diameter) under a hydrogen pressure of 40 kg./cm. G, a temperature of 380 C., and an oil feed rate of 50 1it./hr.
  • the hydrorefined oil had the following properties.
  • the distillation characteristics somewhat differed from that of the material oil since it had been flushed after the reaction in a high temperature gas-liquid separator so as to remove high boilers.
  • the hydrorefined oil was then reacted with ethylene under a reaction pressure of l g./cm. G, at an oil feed rate of 50 liters/hr., and an ethylene to oil molar ratio of from 3 to 5 using a silica-alumina catalyst (3 mm. in diameter).
  • the properties of the reaction product thus obtained were as follows:
  • the resultant product had reduced aromatic protons and increased methylenes attached to the aromatic as well as methyl protons in comparison to the material. This indicates clearly the addition of ole'fin to aromatics.
  • the efiluent product oil thus treated according to the above procedure had a markedly increased transparency.
  • the hydrogenated product had the following distillation properties:
  • fractions than the fraction boiling at 260 to 350 C. exhibited characteristic properties and were found to be utilizable suitably as paint vehicles, plasticizers and as jet engine fuels.
  • propylene was reacted with the refined oil using a silica-alumina catalyst under a pressure of 8 kg./cm. G, at a temperature of from 200 to 250 C. and at an oil flow rate of 2 1it./hr. using a reaction tube of a diameter of 20 mm.
  • the product showed an increase in the 50% distill-off point of about 70 C. and a decrease of nearly 0.058 in the specific gravity at 15 C.
  • the product oil was found to exhibit better electrical properties than the product obtained by reacting with ethylene according to Example 1.
  • the resultant product was then nuclear hydrogenated using a nickel diatomaceous earth catalyst diluted with an equal amount of aluminum grain at a hydrogen pressure of 100 kg./cm. G, a reactor inlet temperature of 170 C. a reactor outlet temperature of 280 C. and at an oil flow rate of 2 liters/hr.
  • the effluent oil was returned to the reactor so as to make a total time of contact with the nickel-diatomaceous of one hour.
  • the transparency of the oil increased as the sum total of the contact time increased.
  • the 50% distillation point was about 75 C. lower than that of the product oil.
  • the thus obtained hydrogenated product was also found to be desirable as an electrical insulating oil based on the following electric properties.
  • EXAMPLE 3 It has been found that the correlation between the specific gravity of the product and the average number of added olefins has a nearly linear relationship, although it dilfers somewhat depending upon the type of the feed stock.
  • the average number was calculated by analyzing the number of olefins added to the material with (various data obtained by NMR analysis, H/C ratio, mass spectrum analysis and gas chromatography after reacting the olefin at a variety of degrees with the unreacted material which has been previously measured to determine its specific gravity. Accordingly, the degree of the deactivation can be estimated by comparing the difference of the specific gravity between the material and the product at the initial stage of the catalyst with that at the intermediate and at the last stage of the catalyst.
  • Seria crude oil was thermally cracked at 1050 C. at a contact time of 5X10" seconds by using a high temperature stream to give a by-product heavy oil from which a fraction having an initial boiling point of 178 C. and a distill-01f point of 370 C. was obtained and used as the material for imparting thermal stability and successively for the hydrorefining treatment.
  • the catalyst used in this thermal stability-imparting step was a reduced and activated one, identical to the one described in Example 1, and prepared by passing for 20 minutes a hydrorefined oil obtained in Example 1 and containing an added 2 mole percent of dibutyl sulfide, under a pressure nearly equal to atmospheric at a rate of 20 liters per hour for 4 hours while controlling the catalyst temperature all over the reactor to within the range of 80 C.:2 C., then allowing to stand for additional 2 hours followed by treating again with the hydrorefined oil at the same rate for an hour.
  • the following hydrorefining treatment was carried out under a hydrogen pressure of 30 kg./cm. G, at a temperature of 400 C. and at the liquid residence time of 1.0 hour using a cobalt-molybdenum catalyst.
  • the hydrorefined oil thus obtained was adsorptively treated with a low temperature grade activated clay of a particle size of 10 to 30 mesh which had been previously dried at 200 C. with hot air.
  • the acid content of this low temperature-grade activated clay was 0.1 rneq./g. determined according to an amine titration method using di'methyl yellow as an indicator.
  • This adsorptive treatment was carried out at a temperature of C. at a flow rate of the refined oil of 50 volumes per volume of the activated clay.
  • the thus treated oil contained 2.7 p.p.m. by weight of basic nitrogen-containing compounds (calculated as nitrogen) and 45 p.p.m. of sulfur compounds (calculated as sulfur).
  • the oil was then reacted with ethylene at 300 C., under a pressure of 30 kg/cm. G, at a liquid residence time of 0.5 hr., at an ethylene to oil molar ratio of from 3 to 6 in the presence of a Si'O -Al O catalyst having an A1 0 content of about 25 Wt. percent, an acid content of 0.55 meq./ g. and shaped in a size of from 0.5 to 1.5 mm. in diameter and from 3 to 5 mm. length by extrusion, followed by calcinating at 600 C.
  • the relation of the oil feed multiple number to the reaction result was as follows:
  • Feed oil multiple number (Cumulative volume of the oil fed per volume of the catalyst): Reaction result As can be seen from the above results a smooth reaction of ethylene can be effected for a prolonged period.
  • EXAMPLE 4 Light naphtha was thermally cracked at a temperature of 950 C. in an atmosphere of steam with a residence time of 0.2 second to give a liquid product which was used as the feed stock of this example. This material was successively treated in a step for imparting thermal stability, a step of hydrorefining and a step of hydrogenation to thereby produce a nuclear hydrogenated product.
  • the properties of the liquid feed stock were as follows:
  • the stabilized oil was passed through two reactors connected in series each containing 25 liters of a cobaltmolybdenum-alumina catalyst under a reaction pressure of 40 kg./cm. G, an average temperature of 400 C., an oil feed rate of 45 liters/hr., and hydrogen feed rate of 60 Nm. /hr. so as to effect hydrorefining.
  • the sulfur content of the resultant hydrorefined oil showed a reduction to 32 p.p.m. By analysis, it was found that this sulfur was not present as compounds such as hydrogen sulfide, carbon disulfide, mercaptan sulfides, disulfides, polysulfides or thiophene.
  • This hydrorefined oil was further hydrogenated using a packed nickel-diatomaceous earth catalyst.
  • This catalyst was prepared by a preliminary reduction with hydrogen at 160 C. for 6 hours, thereafter the hydrogen was discontinued and the temperature was increased to 260 C. while passing the refined oil at the rate of 50 liters/hr. for 12 hours. Then the hydrogenating reaction was started by gradually increasing the pressure to 100 kg./cm. G while compressing the hydrogen at a temperature of from 260 to 300 C.
  • the resultant hydrogenated oil had a markedly higher transparency than that of the starting material.
  • the degree of nuclear hydrogenation determined by the refractive index, the nuclear magnetic resonance spectrum (NMR), a H/ C analysis and the like was 96.5% and the properties of the hydrogenated product were as follows:
  • a process for the preparation of hydrocarbon oils of improved quality by treatment of by-product heavy fractions having an initial boiling point of above 160 C. and a 75% distill-off point of below 450 C. and obtained in the production of gaseous olefins by the thermal cracking of hydrocarbons at temperatures above 700 C. which comprises 1) treating by-product heavy fractions with hydrogen at a temperature of from 40 to 200 C., a pressure of from 5 to 300 kg./cm. G and a liquid residence time of from 0.1 to 5.0 hours in the presence of a nickel-containing catalyst, said catalyst being prepared by treatment with organic sulfur compounds consisting exclusively of carbon, hydrogen and sulfur atoms to obtain thermally stabilized heavy fractions,
  • said olefin being reacted at a temperature of from 40 to 380 C., a pressure of from 0 to kg./cm. G and a liquid residence time of from 0.1 to 5 .0 hours in the presence of a solid acid catalyst.
  • hydrocarbons are petroleum hydrocarbons selected from the group consistin of crude oil, asphalt, fuel oil, kerosene, naphtha and liquefied petroleum gas.
  • said nickel-containing catalyst of Step (1) is prepared by contacting a solid catalyst containing at least 1% by weight reduced nickel with said organic sulfur compounds at a temperature below 150 C. in a ratio of at least 0.01 sulfur atom per nickel atom, then allowing the catalyst to stand for at least 10 seconds.
  • said nickel-containing catalyst of Step (1) contains at least 1% by weight of reduced nickel and not more than 10% by weight, based on the nickel, of a promoter consisting of copper and chromium.
  • said solid acidic substance is selected from the group consisting of activated clay, silica-alumina and solid phosphoric acid.
  • said solid acid catalyst is selected from the group consisting of silicaalumina, silica-magnesia, alumina-boria, crystalline aluminosilicate, nickel oxide-silica, silver oxide-silica-alumina and solid phosphoric acid.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US97231A 1969-12-11 1970-12-11 Process for treating by-product heavy fractions formed in the production of olefins Expired - Lifetime US3689401A (en)

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JP9904669A JPS4925404B1 (enrdf_load_stackoverflow) 1969-12-11 1969-12-11
JP1134270A JPS4843887B1 (enrdf_load_stackoverflow) 1970-02-09 1970-02-09
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BE (1) BE760226A (enrdf_load_stackoverflow)
CA (1) CA936821A (enrdf_load_stackoverflow)
FR (1) FR2070817B1 (enrdf_load_stackoverflow)
GB (1) GB1323105A (enrdf_load_stackoverflow)
NL (1) NL157348B (enrdf_load_stackoverflow)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951780A (en) * 1974-10-25 1976-04-20 Exxon Research And Engineering Company Aromatic oils by thermal polymerization of refinery streams
US5045174A (en) * 1990-03-21 1991-09-03 Exxon Chemical Patents Inc. Process for the production of heartcut distillate resin precursors
US20040104147A1 (en) * 2001-04-20 2004-06-03 Wen Michael Y. Heavy oil upgrade method and apparatus
US20040176652A1 (en) * 2003-03-04 2004-09-09 Michel Molinier Dual bed process using two different catalysts for selective hydrogenation of acetylene and dienes
US20040176651A1 (en) * 2003-03-04 2004-09-09 Michel Molinier Catalysts for selective hydrogenation of alkynes and alkadienes
US20080223753A1 (en) * 2007-03-14 2008-09-18 Florent Picard Method for desulfurizing hydrocarbon fractions from steam cracking effluents
US20090247800A1 (en) * 2008-03-31 2009-10-01 Air Products And Chemicals, Inc. Process for Hydrogenating Olefins
WO2024086076A1 (en) * 2022-10-17 2024-04-25 Lummus Technology Llc Selective treatment of fcc gasoline for removal of sulfur, nitrogen, and olefin compounds while maximizing retention of aromatic compounds

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3437702A (en) * 1967-04-03 1969-04-08 Sun Oil Co Method for treating cracked gas oil
US3481996A (en) * 1968-12-04 1969-12-02 Sun Oil Co Process for hydrodesulfurization of cracked gas oils and the production of dimethyldecalins and fuel oil blending components

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951780A (en) * 1974-10-25 1976-04-20 Exxon Research And Engineering Company Aromatic oils by thermal polymerization of refinery streams
US5045174A (en) * 1990-03-21 1991-09-03 Exxon Chemical Patents Inc. Process for the production of heartcut distillate resin precursors
US20040104147A1 (en) * 2001-04-20 2004-06-03 Wen Michael Y. Heavy oil upgrade method and apparatus
US20040176652A1 (en) * 2003-03-04 2004-09-09 Michel Molinier Dual bed process using two different catalysts for selective hydrogenation of acetylene and dienes
US20040176651A1 (en) * 2003-03-04 2004-09-09 Michel Molinier Catalysts for selective hydrogenation of alkynes and alkadienes
WO2004078888A1 (en) * 2003-03-04 2004-09-16 Exxonmobil Chemical Patents Inc. Catalysts for selective hydrogenation of alkynes and alkadienes
US7038097B2 (en) 2003-03-04 2006-05-02 Exxonmobil Chemical Patents Inc. Dual bed process using two different catalysts for selective hydrogenation of acetylene and dienes
US7153807B2 (en) 2003-03-04 2006-12-26 Exxon Mobil Chemical Patents Inc. Catalysts for selective hydrogenation of alkynes and alkadienes
US20080223753A1 (en) * 2007-03-14 2008-09-18 Florent Picard Method for desulfurizing hydrocarbon fractions from steam cracking effluents
FR2913692A1 (fr) * 2007-03-14 2008-09-19 Inst Francais Du Petrole Procede de desulfuration de fractions hydrocarbonees issues d'effluents de vapocraquage
EP1972678A1 (fr) * 2007-03-14 2008-09-24 Ifp Procédé de désulfuration de fractions hydrocarbonées issues d'effluents de vapocraquage
US7947166B2 (en) 2007-03-14 2011-05-24 IFP Energies Nouvelles Method for desulfurizing hydrocarbon fractions from steam cracking effluents
CN101265421B (zh) * 2007-03-14 2013-03-27 Ifp公司 蒸汽裂化流出物烃馏分的脱硫方法
US20090247800A1 (en) * 2008-03-31 2009-10-01 Air Products And Chemicals, Inc. Process for Hydrogenating Olefins
US8664459B2 (en) * 2008-03-31 2014-03-04 Air Products And Chemicals, Inc. Process for hydrogenating olefins
WO2024086076A1 (en) * 2022-10-17 2024-04-25 Lummus Technology Llc Selective treatment of fcc gasoline for removal of sulfur, nitrogen, and olefin compounds while maximizing retention of aromatic compounds

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DE2061137B2 (de) 1976-05-13
CA936821A (en) 1973-11-13
SU532344A3 (ru) 1976-10-15
FR2070817B1 (enrdf_load_stackoverflow) 1974-02-15
BE760226A (fr) 1971-05-17
GB1323105A (en) 1973-07-11
FR2070817A1 (enrdf_load_stackoverflow) 1971-09-17
NL7018075A (enrdf_load_stackoverflow) 1971-06-15
DE2061137A1 (de) 1971-08-05
NL157348B (nl) 1978-07-17

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