US1960951A - Method of converting by catalysis mineral and vegetable oils - Google Patents

Method of converting by catalysis mineral and vegetable oils Download PDF

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US1960951A
US1960951A US593690A US59369032A US1960951A US 1960951 A US1960951 A US 1960951A US 593690 A US593690 A US 593690A US 59369032 A US59369032 A US 59369032A US 1960951 A US1960951 A US 1960951A
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mineral
vegetable oils
carbonized
converting
activated carbon
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US593690A
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Oppenheim Rene
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Mersen SA
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Le Carbone Sa
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • C10G2300/1014Biomass of vegetal origin
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006Temperature
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This invention relates to an improvement in or modification of the process set forth in the specification of the patentof F. C. F. Portail, No. 1,842,197 bearing the date of January 19, 1932.
  • the invention forming the subject matter of said parent patent of Portail consists in the conversion of mineral and vegetable oils in order to obtain lighter products, by catalysis by the action of activated carbon.
  • said blocks being, if required, pierced by channels.
  • the subject matter of the present application is an improvement in the aforesaid process, which consists essentially in forming the catalyst of an entanglement or a fabric of carbonized fibres.
  • This product may be used either alone or combined with a suitable support, upon which it may be spread, wound, etc. It may also be provided with a reinforcement to support it.
  • a characteristic method of applying the reinforcement consists in incorporating it intimately in the product, for example by introducing it into the prod,- uct during the preparatory matting or weaving. It is thus possible to employ at the same time in the weaving threads that aretobe carbonized and other threads of products which do not carbonize and which subsequently form the reinforcement of the fabric.
  • the single figure of the drawing illustrates in section and only by way of example a vertical cross-section of an installation for carrying out the process according to the 'vention.
  • the reservoir b contains th oil to be treated.
  • a compressor a is connected tothe upper portion of reservoir 1) and creates an air pressure.
  • each member 0 contains a felted or woven mass of carbonized and activated fibres which of course increase in section toward header 0" as said mass fills the interior of such memher 0.
  • the output of such tubes or chambers which are a hundred millimeters in diameter is approximately fifty or more liters per hour each, the reaction tubes c'forming catalyzing chambers due to the presence of the fibrous activated carbon 1.
  • the treated liquid is conducted by a pipe g from the header 0" into a pressure reducing chamber a, from whence the light products are conducted through the coil of a condenser it into a receptacle 2'.
  • the non-condensable constituents of the oil are discharged by a pump 7' to be used in appropriate manner.
  • the fibrous activated carbon may be manufactured according to known methods which are not necessarily in themselves part of the invention. but the following methods for preparing suchproduct may be noted.
  • the fibrous product may initially be in. the form of a strip wound on a core of carbon for example, or on an end of a tube etc., so that the whole, after winding, forms a block; the roll formed may then, if desired, be enclosed in a metallic box.
  • the strip may also be arranged as a fiat coil. It is also possible to replace it by a pile of discs or rings.
  • the practical embodiment may consist of a simple pile of pieces of cotton wool activatedin a tube; this enables a uniform mass of entangled fibres to beobtained.
  • the block or mass of carbonized fibres formed as just described is placed in a suitable envelope and is supported by its reinforcement or by any suitable means, for example by plates of porous carbon, by metallic pieces,'etc.
  • the activated carbon formed as just described presents special advantages.
  • the activated cotton wool or fabrics have a porosity which is very superior to that of the agglomerated blocks described in the patent of Portail.
  • a column of cotton wool or of fabric arranged in a pipe causes a loss of pressure that is much smaller than that caused by a solid block of activated carbon.
  • the great plasticity of the activated cotton wool enables the interstices, through which the liquid to be treated could fiow away without being absorbed by the carbonized and activated cotton wool, to be eliminated by a suitable heaping thereof in the vessel in which the treatment is to be carried out. There is thus ensured an intimate contact between the liquid to be treated and the catalyst, which enables the yield of the operation to be considerably improved.
  • the gas obtained may be used for any suitable purposes and in particular for heating the activated carbon and the fractionated distilling apparatus.
  • Process for catalytically transforming or converting mineral and vegetable oils which consists in exposing the same at an elevated temperature ranging from about 300 to about 350 to the action of activated carbon in the form of entangled and interlocated fibres of vegetable origin suitably carbonized and activated, which are distinct, long, flexible and resistant so' as to constitute in their aggregate, a highly porous mass of changeable and plastic form.
  • Process for catalytically transforming or converting mineral and vegetable oils which consists in exposing the same at an elevated temperature ranging from about 300 to about 350 to the action of activated carbon in the form of entangled, interlaced and woven carbonized fibres of vegetable origin such as a wick of cotton fabric, suitably carbonized and activated, which carbonized fibres are distinct, long, flexible and resistant so as to constitute in their aggregate, a highly porous mass of changeable and plastic form.

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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)
  • Inorganic Fibers (AREA)

Description

R. OPPENHEIM May 29, 1934.
METHOD OF CONVERTING BY UA'IALYSIS MINERAL AND VEGETABLE OILS Filed Feb. .17, 1932 Patented May 29, 1934 METHOD OF CONVERTING BY GATALYSIS MINERAL AND VEGETABLE OILS Rene Oppenheim, Gennevilliers, France, assignor to Socit Anonyme le Car-bone, Gennevflliers,
France Applicatiorin February 17, 1932,
Serial No. 593.690
France January 22, 1
v 3 Claims.
This invention relates to an improvement in or modification of the process set forth in the specification of the patentof F. C. F. Portail, No. 1,842,197 bearing the date of January 19, 1932.
5 The invention forming the subject matter of said parent patent of Portail consists in the conversion of mineral and vegetable oils in order to obtain lighter products, by catalysis by the action of activated carbon.
It is indicated in the specification of the patent of Portail that it is advantageous to agglomerate the activated carbon into blocks through which the oils that are to be converted are passed, the
said blocks being, if required, pierced by channels.
' The subject matter of the present application is an improvement in the aforesaid process, which consists essentially in forming the catalyst of an entanglement or a fabric of carbonized fibres.
By way of example, there may be mentioned as suitable for the new use the carbonized fabric of lamp wick or carbonized cotton wool.
In order" to improvethe quality of the product and so render more effective the decomposition of the hydrocarbons on which it is to actythe product is treated in accordance with the known activation processes in order that the carbon of which it is formed may be activated. But first cotton or other such fibers are connected by matting them into a sort ofwool or else weaving the same together to forma fabric, either form being later carbonized and activated.
This product may be used either alone or combined with a suitable support, upon which it may be spread, wound, etc. It may also be provided with a reinforcement to support it. A characteristic method of applying the reinforcement consists in incorporating it intimately in the product, for example by introducing it into the prod,- uct during the preparatory matting or weaving. It is thus possible to employ at the same time in the weaving threads that aretobe carbonized and other threads of products which do not carbonize and which subsequently form the reinforcement of the fabric.
The single figure of the drawing illustrates in section and only by way of example a vertical cross-section of an installation for carrying out the process according to the 'vention.
The reservoir b contains th oil to be treated. A compressor a is connected tothe upper portion of reservoir 1) and creates an air pressure.
lar to c are disposed within the heating chamber d and are heated by a plurality of burners c, said reaction tubes 0 are located and connected in parallel between headers c andc", all mounted within heating chamber d, and which on such l form has to increase in' section toward the cylinder 0'. Each member 0 contains a felted or woven mass of carbonized and activated fibres which of course increase in section toward header 0" as said mass fills the interior of such memher 0. The output of such tubes or chambers which are a hundred millimeters in diameter is approximately fifty or more liters per hour each, the reaction tubes c'forming catalyzing chambers due to the presence of the fibrous activated carbon 1.
The treated liquid is conducted by a pipe g from the header 0" into a pressure reducing chamber a, from whence the light products are conducted through the coil of a condenser it into a receptacle 2'. The non-condensable constituents of the oil are discharged by a pump 7' to be used in appropriate manner.
The fibrous activated carbon may be manufactured according to known methods which are not necessarily in themselves part of the invention. but the following methods for preparing suchproduct may be noted.
. The fibrous product may initially be in. the form of a strip wound on a core of carbon for example, or on an end of a tube etc., so that the whole, after winding, forms a block; the roll formed may then, if desired, be enclosed in a metallic box. The strip may also be arranged as a fiat coil. It is also possible to replace it by a pile of discs or rings.
The practical embodiment may consist of a simple pile of pieces of cotton wool activatedin a tube; this enables a uniform mass of entangled fibres to beobtained. I
The block or mass of carbonized fibres formed as just described is placed in a suitable envelope and is supported by its reinforcement or by any suitable means, for example by plates of porous carbon, by metallic pieces,'etc.
The activated carbon formed as just described presents special advantages. The activated cotton wool or fabrics have a porosity which is very superior to that of the agglomerated blocks described in the patent of Portail. A column of cotton wool or of fabric arranged in a pipe causes a loss of pressure that is much smaller than that caused by a solid block of activated carbon.
Moreover, owing to the very great plasticity of the activated cotton wool, it is possible to regulate very eflicaciously the porosity of the layer of carbon and, consequently, the period of contact between the liquid to be treated and the active carbon..
Finally, the great plasticity of the activated cotton wool enables the interstices, through which the liquid to be treated could fiow away without being absorbed by the carbonized and activated cotton wool, to be eliminated by a suitable heaping thereof in the vessel in which the treatment is to be carried out. There is thus ensured an intimate contact between the liquid to be treated and the catalyst, which enables the yield of the operation to be considerably improved.
The manner of using the apparatus already described in order to carry out the process may be varied according to the oils which are to be treated and according to certain laboratory tests which have already been indicated in the above mentioned patent of Portail and given by way of example below:
By passing gas oil containing 75% of products distilling above 250 C. through the activated carbon, it was found that decomposition took place as soon as the temperature of the catalyzer reached 300 C.
At 350 C. there were obtained about:
35% of combustible gases (gas with a great calorific power of 15,000 caloriestper cubic meter approximately.
The liquid residue (65%) subjected to fractionated distillation gave:
6% spirit at temperatures up to 110 C. 6% spirit at temperatures from 110 to 150 C.
9% spirit at temperatures from 150 to 200 C.,
and 20% liquid at temperatures from 200 to 250 C.
In both cases the final liquid residue, that is to s y. 1
24% in the first case and 1 17% in the second may be passed again over the activated carbon and again furnish light volatile spirits. The' final results after this second passage comprise 90% of products distilling below 250 C.
Actual tests also indicate that vegetable oils may be cracked by passing the same through felted or woven fibrous activated carbon. The results of a test on peanut oil follow:
fractionated distillation were obtained:
100 c. c. of peanut oil were passed through activated carbon and the following results of c. c. Gas, non-condensible at 0 C 20.2 Liquid 53.0
of which 18 c. c. distill under 150 C., 14 c. 0. distill between 150 and 235 C. and 21 c. 0. do not distill at 235.
The different figures given above are, as will be understood, merely given by way of an indication and will vary according to the nature of the product treated, the speed of passage of this product, the cooling temperature of the products distilled and, finally, the nature of the activated carbon used as catalyzer, which is here a felted or. woven fibrous mass.
It is furthermore remarked that the gas obtained may be used for any suitable purposes and in particular for heating the activated carbon and the fractionated distilling apparatus.
The arrangements described above are only given by way of example; all the details of performing the new improvement and o carrying it into effect maybe varied without changing the principle of the invention.
Having now fully described my invention and indicated a. practical manner of carrying the same out in practice, I claim:
1. Process for catalytically transforming or converting mineral and vegetable oils, which consists in exposing the same at an elevated temperature ranging from about 300 to about 350 to the action of activated carbon in the form of entangled and interlocated fibres of vegetable origin suitably carbonized and activated, which are distinct, long, flexible and resistant so' as to constitute in their aggregate, a highly porous mass of changeable and plastic form.
2. Process for catalytically transforming or converting mineral and vegetable oils, which consists in exposing the same at an elevated temperature ranging from about 300 to about 350 to the action of activated carbon in the form of entangled, interlaced and felted carbonized fibres of vegetable origin such as, suitable carbonized and activated cotton wool,'which carbonized fibres are distinct, long, flexible and resistant so as to constitute in their aggregate, a
highly porous felted mass of changeable and plastic form.
3. Process for catalytically transforming or converting mineral and vegetable oils, which consists in exposing the same at an elevated temperature ranging from about 300 to about 350 to the action of activated carbon in the form of entangled, interlaced and woven carbonized fibres of vegetable origin such as a wick of cotton fabric, suitably carbonized and activated, which carbonized fibres are distinct, long, flexible and resistant so as to constitute in their aggregate, a highly porous mass of changeable and plastic form.
RENE- oPPENnEm.
US593690A 1932-01-22 1932-02-17 Method of converting by catalysis mineral and vegetable oils Expired - Lifetime US1960951A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2459907A (en) * 1942-09-04 1949-01-25 Nat Carbon Co Inc Method of conducting chemical reactions
US3041377A (en) * 1958-11-17 1962-06-26 Harast Joseph Manufacture of aromatic amines from nitro compounds
US3094479A (en) * 1958-02-07 1963-06-18 Sweeney Maxwell Patrick Conversion process and apparatus
EP1489157A1 (en) * 2003-06-16 2004-12-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for converting of raw materials and waste materials containing oil or fat in a composition containing hydrocarbons, products produced by this method and their application
DE102005023601B4 (en) * 2005-05-18 2008-03-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the continuous or semi-continuous conversion of fatty or oily raw materials and waste into mixtures with a high hydrocarbon content, products produced by this process and their use
DE102008049778A1 (en) 2008-09-30 2010-04-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the recovery of gaseous hydrocarbons from biogenic raw materials
DE102008060558A1 (en) * 2008-12-04 2010-06-10 Eduard Buzetzki Process for the catalytic cracking of vegetable oils and animal fats
WO2013053754A1 (en) * 2011-10-10 2013-04-18 Fraunhofer-Ges. Zur Förderung Der Angewandten Forschung E.V. Method for extracting hydrocarbons with medium chain lengths, and the use of same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2459907A (en) * 1942-09-04 1949-01-25 Nat Carbon Co Inc Method of conducting chemical reactions
US3094479A (en) * 1958-02-07 1963-06-18 Sweeney Maxwell Patrick Conversion process and apparatus
US3041377A (en) * 1958-11-17 1962-06-26 Harast Joseph Manufacture of aromatic amines from nitro compounds
EP1489157A1 (en) * 2003-06-16 2004-12-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for converting of raw materials and waste materials containing oil or fat in a composition containing hydrocarbons, products produced by this method and their application
DE102005023601B4 (en) * 2005-05-18 2008-03-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the continuous or semi-continuous conversion of fatty or oily raw materials and waste into mixtures with a high hydrocarbon content, products produced by this process and their use
DE102008049778A1 (en) 2008-09-30 2010-04-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the recovery of gaseous hydrocarbons from biogenic raw materials
US20110237854A1 (en) * 2008-09-30 2011-09-29 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Method for extracting gaseous hydrocarbons from biogenic raw materials
US8686210B2 (en) 2008-09-30 2014-04-01 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Method for extracting gaseous hydrocarbons from biogenic raw materials
DE102008060558A1 (en) * 2008-12-04 2010-06-10 Eduard Buzetzki Process for the catalytic cracking of vegetable oils and animal fats
DE102008060558B4 (en) * 2008-12-04 2013-09-26 Eduard Buzetzki Process for the catalytic cracking of vegetable oils and animal fats
WO2013053754A1 (en) * 2011-10-10 2013-04-18 Fraunhofer-Ges. Zur Förderung Der Angewandten Forschung E.V. Method for extracting hydrocarbons with medium chain lengths, and the use of same
US9840447B2 (en) 2011-10-10 2017-12-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for extracting hydrocarbons with medium chain lengths, and the use of the same

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