US2824148A - Preparation of olefins - Google Patents

Preparation of olefins Download PDF

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Publication number
US2824148A
US2824148A US430404A US43040454A US2824148A US 2824148 A US2824148 A US 2824148A US 430404 A US430404 A US 430404A US 43040454 A US43040454 A US 43040454A US 2824148 A US2824148 A US 2824148A
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cracking
zone
weight
temperature
heating zone
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Expired - Lifetime
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US430404A
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English (en)
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Keulemans Aloysius Ignat Marie
Kwantes Arien
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Shell Development Co
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Shell Development Co
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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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C10G9/38—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours produced by partial combustion of the material to be cracked or by combustion of another hydrocarbon
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • This invention relates to the preparation of oleiins, and particularly to the production of olens by the cracking of high boiling hydrocarbons.
  • Another drawback is that-especially when it is desired to obtain high yields of nonbranched oleins from starting materials containing predominantly normal paraiiins-the time required to raise the material to be cracked to the cracking temperature should be so selected as to be as short as possible to avoid undesirable changes in the initial material, and that when high temperature gradients are employed to this end, there is the danger of overheating the starting material, with the result that nevertheless undesirable reactions may occur.
  • Combustion may be eiected by any suitable gas which sustains combustion, such as oxygen or free oxygen-containing gases, particularly air, or other gases having an ⁇ oxidizing effect, such as nitrogen oxides or ozone, or
  • The-partofthe starting material'which is burned will vary with the cracking temperature to be applied and the degree of cracking. In general combustion of not more than about to 15% by weight of the supplied material willsutlice.
  • suitable substances'which promote oxidation include'those having aY largeactive surface area, for instance, an areaof more than 40 square-metersfper gram, such as activated alumina; bauxite, silica gel, titanium oxide, cerium oxide, thorium.oxide, ⁇ chromium trioxidevanadium pentoxide, oxides of1 cobalt or manganese, or mixtures or: combinations of two or more of these substances. It is preferable to useV a strongfoxida-k tioncatalyst, for example, vanadium pentoxide, which is suitably applied to a carrierrsuchas activated alumina,
  • silica gelfragments madefrom bauxite, silicates, etc.
  • the heating andthe cracking spaces can be madefrom comparatively cheap materials, such as ordinary steel, theheating space being'conveniently provided on its insidev with arefractory lining.
  • any type of high boiling hydrocarbon mixture i. e., any type of high boiling hydrocarbon mixture (i. e.,
  • the aromatic content is readily determined by per@ colating a sample ofthe hydrocarbon mixture over silica gel .and then, desorbing: the non-aromaticsV by Washingfthe silica gel.with.a. low boiling. saturated hydrocarbon, for example n-:hexane,.after which the portion of the sample left7 orr the silica gelis regarded. asy aromatics.
  • Thefcomposition ofthefnon-aromatic'part of the initial material which may consist of normal: parains, isoparafns and naphthenes, is ofA secondary importance if it: isl intendedi toV prepare mainly olefins with lower molecular weight, that is to say, with less than 6 carbon atoms per molecule. However, this is not the case when it-is desired to produce mainly higher olens.
  • the starting material should have a content of higher paraffin molecules or radicals of more than 40% by weight, preferably more than 60% by weight.
  • parans may not only occur as normal alkanes butalso intheform'ofstraight chains which are boundtohydrocarbons ofdifferentstructure, for instance as in a higher n-alkylnaphthene.
  • suitable initial ⁇ materials are. high' boiling, mineral oi-l :fractions-poor. in aromatics, or Fischer-Tropsch higher. hydrocarbons,V paratn waxdistillates or other material rich in paraffin wax such as paraffin wax obtained when dewaxing lubricating oils, and the like.
  • a special advantage of the process of the invention is that it provides a method whereby cheap initial materials which are abundantly available may be used as starting material, such as residues boiling above 450 C. which are obtained when distilling mineral oils or mineral oil products, and which could not be processed'inthe vapor phase cracking processes heretofore employed.
  • the starting material to be converted may. be. conveniently preheated, decomposition with the'formationof carbon deposits being preferably avoided. If the-starting material is not liquid, owing to the presence of normally solid parans, it must be sufliciently preheated to liquefyxit.
  • the temperature at which the starting material is heated in the heating zone and also theL residence time of the vapor mixture effluent from that zone in the cracking zone will depend on the natureof: the olelins whichare desired to be prepared.
  • crackingtemperaturesin the range from 650 C. to 900 C., preferably' from 700 C. to 800 C.
  • residence' times inthe cracking space varying'from 3 to 0.001 ⁇ secends, preferably from l' to-0.-2 ⁇ second, areused. Accordingly as the crackingtemperature is-selected"higher, the,
  • the residencek time may be adjusted, within the desired limits by means of the throughput rate.v
  • Vreaction producteluentifr'omthe .cracking zone being thenquickly cooled. or quenched; whichisrconveniently eifected by direct. contact with: a ⁇ coolant,.forinstance, water,,cooledinertrefractory pebbles, cooled inertv finely divided refractory material ina fluidized bed, and thelike:
  • the processrof the. ⁇ invention yields products which are rich in ⁇ olens andv consist mainlyofl lower olefins such4 as ethene, propene, butenes and the like (which-may be' convertedintovaluable derivatives'of'various kinds, for example, saturated or unsaturated halohydrocarbons, alcohols, etc.) or consist to a large extent of higherolens which mayalso be used for preparing valuable derivatives;
  • the higher straight-chainolefins forexample, those boilingbetween-about ⁇ C. and 300 C., are an excel-4 asa-4,148
  • lent starting material for the production of secondary sul furie acid alkyl ester salts for instance, secondarysodium alkyl sulfates having an excellent detergency, while the higher branched oleiins, which are also formed, are, for example, suitable for use as initial material for preparing alkyl aryl sultonates possessing also good surface-active properties.
  • Another iield of application of the higher olens obtained by the practice of the invention is the production of products intended for use as lubricating oil additives, for instance, calcium alkylsalicylates.
  • a hydrocarbon feed which may suitably be a paranic oil containing about by weight of aromatics and boiling above 500 C. is passed by line 11 through preheating zone A, in which it may be preheated to 100 C. From zone A, the feed passes in liquid phase through line 12 into heating zone B. Combustion sustaining gas enters the system through line 13 and header 14.
  • the gas which may be, for example, air or oxygen, may be passed directly into heating zone B by opening valve 15 in line 16 or it may be admixed with the hydrocarbon feed ahead of the heating zone by opening valve 18 inline 19 to introduce the gas into line 12.
  • the section of line 12 from the intersection with line 19 to the point at which it enters the heating zone may represent a suitable oil burner.
  • a diluent such as steam, may be added, if desired, by introducing it through line 20 into header 21 from which it may pass to line 12 by opening valve 26 in line 22 or it may pass into heating zone B by opening valve 28 in line 24.
  • a liquid or vaporous oil feed into a combustion zone either in previous admixture with combustion supporting gas or in such a manner that the oil and com# bustion supporting gas are admixed in the combustion zone, and either with or Without the addition of diluent gas.
  • Heating zone B is filled with a bed of particulate oxidation promoting solid, 30, e. g. a catalyst consisting of 95% by weight of activated alumina and 5% by weight of vanadium pentoxide.
  • the catalyst bed may be separated from the cracking zone C by a separating member 31 which may be a Wall with suitable openings to permit passage of the mixture of oil vapors and combustion gases from zone B into Zone C.
  • Cracking zone C will ordinarily be an open space confined by a wall 32 of material resistant to moderately high temperature, e. g. ordinary steel.
  • heating zone B will be coniined by a wall of high temperature resistant material, e. g. ordinary steel which may be lined with a refractory material such as re brick.
  • the mixture of combustion gases and oil vapors is retained in the cracking zone C for a sufficient length of time, in the range stated, to produce a substantial amount of olefinic material.
  • the reaction mixture is then withdrawn through line 34, Where it is immediately quenched in quenching zone D by injecting a quench fluid through line 35.
  • the quench fluid may be, for example, liquid water.
  • the quenched mixture is then passed through line 34 to suitable condensation, separation and recovery equipment, not shown, to recover ultimately as product of the operation olenic materials such as normal alkenes.
  • Example I A parafnous oil residue having an aromatic content or" 15% by weight and boiling above 500 C. was preheated to 100 C. and the material thus melted was passed, at the rate of 600 grams per hour, together with 100 liters of oxygen and 360 grams of water per hour, through a heating space iilled with 100 ml. of catalyst Consisting of 95% by weight of activated alumina and 5% by weight of vanadium pentoxide, and which had been preheated to 400 C.
  • the temperature in the catalyst bed rose to 750 C.
  • the vapor mixture ilowing from the heating space passed through a cracking space having a capacity of approximately 800 ml., the residence time therein being 0.4 second and the temperature having dropped to about 700 C. when the effluent iiowed out. In this case there was obtained a product of which 70% by weight boiled below 30 C. This product boiling below 30 C. amounted to 61% by weight, calculated on the starting material.
  • the ethene-ethane fraction was 90% by volume ethene and 10% by volume ethane.
  • the propene and the butene fraction were practically 100% oleiins.
  • Example II A parainous oil residue boiling above 500 C. and having an aromatic content of 10% and consisting for the rest mainly of branched paraiiins, was preheated to 100 C.
  • the temperature in the catalyst bed rose to 620 C.
  • 10% by weight was burned to form water, carbon dioxide and carbon monoxide.
  • the temperature rose thereby in 0.05 second from 100 C. to 620 C. after which the mixture was kept for a further 1.5 seconds in a cracking space having a capacity of about 3 liters, from which it was withdrawn at a temperature of approximately 600 C.
  • Example III As starting material use was made of a paraliinous material boiling between 350 C. and 450 C. (obtained by dewaxing a light lubricating oil fraction) having an aromatic content of 3% by weight and an n-paraiin content of 85% by weight and for the rest consisting of naphthenes and isopara'ins.
  • This material was preheated to 100 C. and passed at the rate of 500 grams per hour, together with 80 liters of oxygen and 300 grams of water per hour, through a heating space filled with 100 ml. of a catalyst consisting of by weight of activated alumina and 5% by weight of vanadium pentoxide.
  • a process for preparingoleiins by cracking high boiling hydrocarbons while suppressing side reactions which comprises passing a high boiling hydrocarbonY mixture containing less than 25% by weight of"aromatics together with a minor proportionof combustion sustaining gas through a relatively small heating zone containinga bed of particulate oxidation-promoting solidrjunder conditions for essentially complete combustion ofa portion of the hydrocarbon mixture and for quickly raising the temperature thereof to at least 500 C., and immediately thereafter passing the resulting mixture@ emuent from the heating zone through an unobstructedcracking zonewhoseV capacity is atleastfeight timesthat of said heating zone for a short residence time therein wherein essentially onlyvthermal cracking conditions are maintained, cooling th'eeluent cracked products from the cracking zone. below crackingl temperature, and-'recovering oleins-from the product.
  • A.- process according to claim 2 wherein saidf oxidation promoting-solid comprises vanadium pentoxide' supported'on a carrier-having a-large-activesurface area.
  • hydro.- carbon. mixture contains more than 40%-by weight of parafnsand no vmore than 15% by weight of aromatics.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US430404A 1953-05-20 1954-05-17 Preparation of olefins Expired - Lifetime US2824148A (en)

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NL753770X 1953-05-20

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US (1) US2824148A (en, 2012)
BE (1) BE528920A (en, 2012)
DE (1) DE1032246B (en, 2012)
FR (1) FR1104908A (en, 2012)
GB (1) GB753770A (en, 2012)
NL (1) NL81937C (en, 2012)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871254A (en) * 1955-10-20 1959-01-27 Shell Dev Olefins from cat-cracked cycle oil
US3006944A (en) * 1960-02-24 1961-10-31 Exxon Research Engineering Co High temperature oxidation
US3156642A (en) * 1960-07-22 1964-11-10 Phillips Petroleum Co Process for conversion of hydrocarbons
US3161696A (en) * 1958-09-06 1964-12-15 Basf Ag Autothermal cracking of hydrocarbons to cracked gas rich in olefines
US3175019A (en) * 1959-11-30 1965-03-23 Phillips Petroleum Co Hydrocarbon conversion
US3536775A (en) * 1969-06-02 1970-10-27 Phillips Petroleum Co Removal of oxygen and oxygenated compounds from unsaturated hydrocarbons
US3541179A (en) * 1966-11-10 1970-11-17 Japan Gasoline Process for manufacturing olefins by catalytic partial oxidation of hydrocarbons

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1111168B (de) * 1958-09-06 1961-07-20 Basf Ag Verfahren zur Herstellung von olefinreichem Spaltgas durch flammenlose Umsetzung von gasfoermigen und/oder verdampfbaren Kohlenwasserstoffen
DE102018000503A1 (de) 2017-07-13 2019-01-17 IP Know UG (haftungsbeschränkt) Anordnung mit elektronischer Zunge
DE202018006920U1 (de) 2017-07-13 2024-08-09 Horst Ahlers Elektrochemischer Toilettensensor

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1295825A (en) * 1918-07-15 1919-02-25 Surface Comb Inc Process of cracking heavy oils.
US1597798A (en) * 1922-07-21 1926-08-31 Clarence P Byrnes Method of treating liquid hydrocarbons
US1935148A (en) * 1927-07-30 1933-11-14 Universal Oil Prod Co Hydrocarbon oil conversion
US2371147A (en) * 1945-03-13 Preparation op unsaturated ali
US2394849A (en) * 1946-02-12 Process for treating hydrocarbons
US2520149A (en) * 1944-06-14 1950-08-29 Koppers Co Inc Process for producing olefins
US2587703A (en) * 1948-02-18 1952-03-04 Universal Oil Prod Co Cracking heavy oils in presence of oxygen
US2595254A (en) * 1941-06-19 1952-05-06 Standard Oil Dev Co Apparatus and process for circulating powdered solid in chemical treatment
US2766308A (en) * 1952-03-21 1956-10-09 Universal Oil Prod Co Method for producing and recovering aromatic hydrocarbons

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR955750A (en, 2012) * 1950-01-19
GB664359A (en, 2012) * 1947-05-30

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2371147A (en) * 1945-03-13 Preparation op unsaturated ali
US2394849A (en) * 1946-02-12 Process for treating hydrocarbons
US1295825A (en) * 1918-07-15 1919-02-25 Surface Comb Inc Process of cracking heavy oils.
US1597798A (en) * 1922-07-21 1926-08-31 Clarence P Byrnes Method of treating liquid hydrocarbons
US1935148A (en) * 1927-07-30 1933-11-14 Universal Oil Prod Co Hydrocarbon oil conversion
US2595254A (en) * 1941-06-19 1952-05-06 Standard Oil Dev Co Apparatus and process for circulating powdered solid in chemical treatment
US2520149A (en) * 1944-06-14 1950-08-29 Koppers Co Inc Process for producing olefins
US2587703A (en) * 1948-02-18 1952-03-04 Universal Oil Prod Co Cracking heavy oils in presence of oxygen
US2766308A (en) * 1952-03-21 1956-10-09 Universal Oil Prod Co Method for producing and recovering aromatic hydrocarbons

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871254A (en) * 1955-10-20 1959-01-27 Shell Dev Olefins from cat-cracked cycle oil
US3161696A (en) * 1958-09-06 1964-12-15 Basf Ag Autothermal cracking of hydrocarbons to cracked gas rich in olefines
US3175019A (en) * 1959-11-30 1965-03-23 Phillips Petroleum Co Hydrocarbon conversion
US3006944A (en) * 1960-02-24 1961-10-31 Exxon Research Engineering Co High temperature oxidation
US3156642A (en) * 1960-07-22 1964-11-10 Phillips Petroleum Co Process for conversion of hydrocarbons
US3541179A (en) * 1966-11-10 1970-11-17 Japan Gasoline Process for manufacturing olefins by catalytic partial oxidation of hydrocarbons
US3536775A (en) * 1969-06-02 1970-10-27 Phillips Petroleum Co Removal of oxygen and oxygenated compounds from unsaturated hydrocarbons

Also Published As

Publication number Publication date
GB753770A (en) 1956-08-01
BE528920A (en, 2012)
DE1032246B (de) 1958-06-19
NL81937C (en, 2012)
FR1104908A (fr) 1955-11-25

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