US2951022A - Preparing lubricating oils using radiation - Google Patents

Preparing lubricating oils using radiation Download PDF

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Publication number
US2951022A
US2951022A US636066A US63606657A US2951022A US 2951022 A US2951022 A US 2951022A US 636066 A US636066 A US 636066A US 63606657 A US63606657 A US 63606657A US 2951022 A US2951022 A US 2951022A
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United States
Prior art keywords
range
viscosity
feed
boiling
radiation
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Expired - Lifetime
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US636066A
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English (en)
Inventor
Harry M Hartzband
Barry L Tarmy
Robert B Long
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to NL109591D priority Critical patent/NL109591C/xx
Priority to NL224273D priority patent/NL224273A/xx
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US636066A priority patent/US2951022A/en
Priority to FR1197772D priority patent/FR1197772A/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/081—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing particle radiation or gamma-radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • this invention proposes a process compnsing irradiating a predomnantly parafiinic feed boiling in the range of about 100 to 700 F. with high energy ionizing radiation at a temperature in the range ahove the pour point of the feed (ca. 50 F.) to 700 F. until at least kilowatt-hours/pound (kW. h./lb.) of radiation have been absorbed to obtain a conversion of at least 1 Wt. percent of the feed per pass.
  • the material so irradiated is then separated to recover an intermediate boiling range (ca. 750/950 F.) lubricating fraction having a viscosity in the range of 35 to 70 SSU at 2l0 F. althougn it can be hi her, and a viscosity index (V.l.) above 120.
  • the material boiling below this interrnediate boiling range fraction is recycled to the radiation zone.
  • the present invention incorporates this surprising finding into a continuous process typified by recovery of a high V.I product.
  • the process of this invention also embodies several other important features.
  • Figure I presents schematically the process of this invention
  • Figure H presents a graph illustrating the unexpected relationship between viscosity and viscosity index of the irradiated product.
  • the feed material for the present nvention boils in the range of 100 to 700 F. -It usually has a viscosity below 35 SSU at 210 F. and is not generally considered a material suitable for lubricating purposes.
  • the feed material used is predominanhy paraflnic. By this is meant it contains at least 75 vvt. percent of parafiinic hydrocarbons. It is preferably 10W in aromatics, both single and condensed ring, i.e., the feed material contains less than 5 wt. percent aromatics. It may contain some oleiins and naphtnenes within the boiling range, but preferably these do not exceed about 25 wt. percent.
  • the feed stock may also contain up to 20 Wt.
  • C C saturates such as Patented Aug. 30, 1960 as Fischer-Tropsch synthesis products, shale oils, and refinery stream such as catalytic cycle stocks.
  • the above described feed material is introduced by line 1 into an irradiation zone 2, to be treated according to this invention with hi h energy ionizing radiation.
  • high energy ionizing radiation is meant radation from terrestrial sources consisting of photons having a wave length less than 50 A. such as gamma and X-rays, rapidly moving charged or uncharged particles of an atomc or subatomic nature having an energy above 30 ev., such as alpha particles and beta rays, and neutrons, the radation heing of sufficient intensity such that the dose rate is at least l. 10 kW. h./lb./hr This excludes radiation such as cosrnic and ultraviolet.
  • lt is rnuch preferred to use radiaton comprising neutrons such as that obtained from a nuclear reactor, so that at least 30% of the energy received is obtained from the neutrons.
  • the feed material is rradiated to an extent adequate to obtain the product characteristics described helow.
  • the material receives a close of at least 5 10" kw. h./ 113., based on fresh feed, and over-irradiation is to be avoided.
  • the maximum amount of radiation usecl should be ander 1 kW. h./lb. based on fresh feed.
  • the ra'te of rradiation is somewhat important. If it is too low, the excited molecules are too dluted to effectively react; and if over-extensive, cracking predominates to polymerzation. While the invention is operable in the range of 1 to 50 10 kw. h./lb./hr. best results are obtained in the range of 4 to 8.
  • the irradiaton can be obtained fIOI1 any convenient source such as charged particle accelerators, e.g. Van de Graaff generators and Betatrons; from nuclear reactors, e.g., atomic piles; waste materials frorn nuclear reactors e.g. spent fuel elements; and materials made radioactive by insertion into a nuclear reactor, e.g., cobalt 60.
  • charged particle accelerators e.g. Van de Graaff generators and Betatrons
  • nuclear reactors e.g., atomic piles
  • waste materials frorn nuclear reactors e.g. spent fuel elements
  • materials made radioactive by insertion into a nuclear reactor e.g., cobalt 60.
  • the use of an atomic pile Wherein mixed gamma and neutron irradiation is obtained is much preferred. This means that the feed material should be substantially free (contain less than 0.5 Wt. percent) of non-hydrocarbon materials that may become radioactive by neutron irradiation
  • the feed material is exposed to the irradiation in any convenient manner.
  • the feed material can smply be flowed through suitable conduits or pipes, in, around, and through the pile.
  • the position of the feed material containng conduits within the pile partially deterrnnes the intensity of rradiation.
  • the pressure during irradiation is not too important, it generally being suflicient to maintain condense phase conditions.
  • Pressures used can range from 0 to 4000 p.s.i.g., or above.
  • the temperature is important. Whle this inventon is operable at temperatures up to about 700 F., best results are obtained at temperatures in the range of 300 to 600 F. Excessively high temperatures result in a loss of product to cracking reactions, and low temperatures may undesirably decrease the reaction rate besides undesirably affecting the product characteristics.
  • pile irradiation which comprises neutrons
  • boren 10 and/or lithium 6 can be added to the feed material to create highly ionzing alpha particls.
  • Cadmium 113 can be used to create highly energetic gamma rays from the neutrons. These materials can exist in amounts in the range of 0.001 to 1 wt. percent as soluble compounds, as discrete subdivided solids,
  • the irradiated material is withdrawn by line 3 before it is over-irradiated, and is separated in zone 4 to recover a product that has a surprisingly high V.I.
  • the products obtained by the irradiation can include dry gas, C s gasoline 430), heating oil (430/600), light lube (600/900), bright stock (900/ 1200), and higher molecular weight polymer.
  • the irradiated product can be separated in zone 4 in any convenient manner. Distillaticn is usually sufficient. A product of suitable viscosity and intermediate boiling range is separated and removed by line 5. This intermediate fraction, boiling in the range of 750950 5., and more preferably 800875 R, is obtained in yields of about 1 to 20 wt. percent per pass, based on fresh feed, and has a viscosity in the rangeof 35 to 70, or above, SSU at 210 F., and a viscosity index of at least 120. With recycle operation ultimate yields of over 80 wt. percent are obtained. t has been observed that the concentration of the desired intermediate boiling range fraction bulds up to a maximum during recycle of about 12 wt. percent. Beyond this the intermediate fraction appears to be converted to heavier material as fast as it is being formed. For this reason, it is desirable that the recovery of the intermediate fraction be such that its concentration in the feed be substantially below 12 wt. percent.
  • the material of lower ooiling range than the product is removed by line 6.
  • the higher boiling material is removed by line 7.
  • the high V.I. product removed by line 5 can, of course, be further treated by other means in separation zone 4 if desired.
  • a molecular type separation as dewaxing, extracticn of aromatics as by silica gel or solvent treating can be used to separate low V.I. components from the high V.I. product.
  • These low V.I. components of about the Same bciling range as the high V.. product. are remmred by line 8.
  • the polymer bottoms in line 7 can be disposed of as desired. They are useful as lubricants of the cylinder or bright stock type, and usually have a viscosity at 210 of 150 SSU or better. either thermally, catalytically, or by irradiation as shown by line 12, to recover some of the over-polymerized feed material, and. the depo-lymerized cracked material can be recycled to zone 2 if desired to be again converted, by itself or witl1 fresh feed, into the proper viscosity range material. 7
  • a separatiorr for a low V.I. product can be made, then They can be subject to cracking the material inline 8 can be recycled and further converted either alone with the feed, or can be combined with the contents of line 7 for thermal cracking. In this way the yield of the process is further increased.
  • Example I 600 cc. of substantially pure cetane (nhexadecane) were irradated in the Brookhaven National Laboratories atomc pile in a vented aluminurn container.
  • the container was maintained at a temperature of 260 F.and at a pressure of abo ut 1 atrn.
  • the flux in the container was about 3 X10 neutrons per square centimeter per second (n/cm. /sec.) and 1.6 megaroentgens/hour of gamma radiation (1 megaroentgen is equivalent to about 1x 10 kw.h./ 1b.
  • the irradiation was continued for about s days until 300 megaroentgens had been absorbed.
  • Example II 42,362 grams of cetane were passed from a storage drum at a rate of 1500 cc./hr. through an aluminurn reactor having an inside diameter of 2 inches and a length of 12 feet.
  • the reactor was located in an unused fuel channel near the center of the Brookhaven pile.
  • the ap proximate flux was 0.2 10 n./cmP/sec. of fast neutrons, 1 10 n./cm?/ sec. of thermal neutrons, and 1 10 R./hr. of gamma rays.
  • the pressure was about atmospheric and the temperature was 200 to 400 F. varying with the length of the reactor.
  • the material from the reactor was passed through a condenser at 65 F.
  • the liquid product was returned to the storage drum for recycle and the gas was metered and vented.
  • the yields, as weight percent on feed, after 3140 hours of operation were:
  • Figure II is aplot of the surprising results obtained from the continuous conversion of cetane.
  • the graph gives the viscosity and viscosity index, as the ordinates.
  • a process comprising irradiating a predorninantly paraffinic feed stock boiling in the range of to 700 F. and having a viscosity below 35 SSU at 210 F. with high energy ionizing radiation having an energy level above 30 electron volts, at a rate in the range of 1 to 50 10- kw. h./lb./hr. and at a temperature up to 700 F. until at least 5 10* kw. h./lb. of radiation are absorbed, separating the material so irradiated and recoverng an intermediate boiling range distillate fraction havng a viscosity above 35 SSU at 210 F. and a V.I.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US636066A 1957-01-24 1957-01-24 Preparing lubricating oils using radiation Expired - Lifetime US2951022A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
NL109591D NL109591C (forum.php) 1957-01-24
NL224273D NL224273A (forum.php) 1957-01-24
US636066A US2951022A (en) 1957-01-24 1957-01-24 Preparing lubricating oils using radiation
FR1197772D FR1197772A (fr) 1957-01-24 1958-01-08 Fabrication d'huiles lubrifiantes en appliquant un rayonnement

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FR (1) FR1197772A (forum.php)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041282A (en) * 1959-04-27 1962-06-26 Shell Oil Co Radiation-resistant lubricant composition
US3043759A (en) * 1956-12-14 1962-07-10 Exxon Research Engineering Co Producing lubricating oils by irradiation
US3153622A (en) * 1959-10-27 1964-10-20 Gulf Research Development Co Irradiation of lubriating oils
WO2007070698A3 (en) * 2005-12-16 2007-12-21 Petrobeam Inc Self-sustaining cracking of hydrocarbons
WO2008080072A3 (en) * 2006-12-22 2008-09-12 Petroradiant Inc Radiation processing of heavy oils

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1627938A (en) * 1927-05-10 Oil distillation and cracking
US2350330A (en) * 1938-09-28 1944-06-06 Theron P Remy Treatment of hydrocarbons with radioactive materials
US2516848A (en) * 1945-10-09 1950-08-01 Electronized Chem Corp Method of producing butadiene from petroleum and petroleum fractions
US2743223A (en) * 1946-08-23 1956-04-24 Leslie T Mcclinton Organic compound bond rupturing process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1627938A (en) * 1927-05-10 Oil distillation and cracking
US2350330A (en) * 1938-09-28 1944-06-06 Theron P Remy Treatment of hydrocarbons with radioactive materials
US2516848A (en) * 1945-10-09 1950-08-01 Electronized Chem Corp Method of producing butadiene from petroleum and petroleum fractions
US2743223A (en) * 1946-08-23 1956-04-24 Leslie T Mcclinton Organic compound bond rupturing process

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3043759A (en) * 1956-12-14 1962-07-10 Exxon Research Engineering Co Producing lubricating oils by irradiation
US3041282A (en) * 1959-04-27 1962-06-26 Shell Oil Co Radiation-resistant lubricant composition
US3153622A (en) * 1959-10-27 1964-10-20 Gulf Research Development Co Irradiation of lubriating oils
WO2007070698A3 (en) * 2005-12-16 2007-12-21 Petrobeam Inc Self-sustaining cracking of hydrocarbons
US20100051444A1 (en) * 2005-12-16 2010-03-04 Zaikin Yuriy A Self-sustaining cracking of hydrocarbons
US8192591B2 (en) 2005-12-16 2012-06-05 Petrobeam, Inc. Self-sustaining cracking of hydrocarbons
EA016698B1 (ru) * 2005-12-16 2012-06-29 Петробим, Инк. Самоподдерживающийся крекинг углеводородов
CN101336283B (zh) * 2005-12-16 2012-09-05 佩特碧姆有限公司 烃的自持裂化
US8911617B2 (en) 2005-12-16 2014-12-16 Petrobeam, Inc. Self-sustaining cracking of hydrocarbons
WO2008080072A3 (en) * 2006-12-22 2008-09-12 Petroradiant Inc Radiation processing of heavy oils
US20090308789A1 (en) * 2006-12-22 2009-12-17 Petroradiant Inc. Radiation processing of heavy oils
US8470166B2 (en) 2006-12-22 2013-06-25 PetroRadiant, Inc. Radiation processing of heavy oils

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Publication number Publication date
NL109591C (forum.php)
FR1197772A (fr) 1959-12-02
NL224273A (forum.php)

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