US3843515A - Countercurrent lube extraction with dual solvent system - Google Patents

Countercurrent lube extraction with dual solvent system Download PDF

Info

Publication number
US3843515A
US3843515A US00234733A US23473372A US3843515A US 3843515 A US3843515 A US 3843515A US 00234733 A US00234733 A US 00234733A US 23473372 A US23473372 A US 23473372A US 3843515 A US3843515 A US 3843515A
Authority
US
United States
Prior art keywords
water
solvent
oil
extraction
pyrrolidone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00234733A
Other languages
English (en)
Inventor
J Macdonald
C Hong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US00234733A priority Critical patent/US3843515A/en
Priority to CA146,957A priority patent/CA978125A/en
Priority to DE2235454A priority patent/DE2235454C2/de
Priority to IT27509/72A priority patent/IT963440B/it
Priority to FR7232603A priority patent/FR2175722B1/fr
Priority to JP9310572A priority patent/JPS568079B2/ja
Application granted granted Critical
Publication of US3843515A publication Critical patent/US3843515A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately

Definitions

  • a solvent comprising N-methyl Z-pyrrolidone' (NMP) and water is contacted with a lube oil feed in order to selectively extract aromatic-type constituents therefrom.
  • the process involves a countercurrent extraction operation and comprises introducing the NMP and water separately into the extraction zone in such a manner that there is no appreciable mixing of the water and NMP with each other prior to the latter, i.e., NMP, contacting the oil.
  • the water is introduced into the extraction zone at a point below the point of introduction of the NMP and either above or below the point of introduction of the oil feed. Results obtained with'this solvent are compared with phenol and phenolwater solvent systems.
  • This invention relates to an improved process for the solvent extraction of an aromatics-containing petroleum oil fraction. More specifically, the process relates to the use of a solvent comprising N-methyl-Z-pyrrolidone and Water to remove at least a portion of the aromatic-type constituents from the lube oil stock. Still more specifically, the process of the invention involves contacting the solvent with the lube oil stock in a countercurrent extraction operation. 1
  • solvent extraction may bev utilized to separate aromatics from lube oil stocks containing aromatics and saturates in order to improve oxidation properties, color, and viscosity index (V.I. of the oil.
  • degree of aromatics separation from a feed stock depends on several factors in addition to the characteristics of the solvent itself, such as the critical solution temperature of the mixture of components and the number of theoretical or actual stages (plates).
  • the critical solution temperature is defined in Chemical Engineers Handbook, McGraw-Hill Fourth Edition, pages 14-44, l963,'as that temperature above which two relatively immiscible liquids become totally miscible with each other.
  • the miscibility of the extract and raflinate phases is directly related to the critical solution temperature.
  • the mutual solubility of the two partially soluble phases increases as the criticalsolution temperature is approached. Above the critical solution temperature the two phases become completely miscible and there is no separation.
  • the temperature is increased, the amounts of oil dissolved in the extract phase and of the solvent dissolved in the rafiinate phase are also increased.
  • the importance of temperature is further shown by the fact that the solvent power always increases with an increase in temperature until complete miscibility is reached,
  • Typical of prior art extraction processes are those utilizing phenol and/or phenol-water solvent systems.
  • One such process is disclosed in US. 2,329,606. Specifically, the process comprises introducing a feed stock into an extraction column and contacting the feed therein with phenol. The phenol is introduced into the top of the column and is contacted therein countercurrently with the upward rising feed stock. Simultaneously, phenolic water is introduced near the bottom of the column.
  • the overall object of the process is to improve the efiiciency of a phenol-water solvent extraction system. This is accomplished by providing internal reflux near the bottom of the column by increasing the selectivity of the solvent at that point.
  • the most preferred solvent system comprises Nmethyl-'2-pyrrolidone in combination with from about 0.5 to about 30% by weight of water, based on total solvent.
  • the process disclosed herein is designed to remove the more polar compounds from a feed consisting of a mixture of hydrocarbons. Specifically, the process is designed to separate the more aromatic type constituents from a feed containing a mixture of said constituents with nonaromatic, or parafiinic and naphthenic hydrocarbons. More particularly, such feeds will consist of petroleum distillate fractions or lube residua (bright stocks). In general, the distillate fractions will have a boiling range within the broad range of about 400 F. to about 1200" F. The preferred distillate fractions are the lubricating oil fractions boiling within the range of 500 F. and 1100 F.,
  • lube residua generally boil above 800 F. These fractions and lube residua may come from any source, such as the parafiinic crudes obtained from Aramco, Kuwait, the Panhandle, North Louisiana, Western Canada and the like.
  • the feed and solvent are contacted in an extraction zone, which may consist of any suitable means to obtain thorough mixing.
  • an extraction zone which may consist of any suitable means to obtain thorough mixing.
  • countercurrent extraction is preferred.
  • the water is injected continuously near the bottom of the countercurrent extractor coming into countercurrent contact with the NMP; the latter being introduced near the top of the extractor, thereby forming an extract phase and a rafiinate phase.
  • the water may be introduced into the extractor either above or below the point of introduction of the feed stock.
  • the two phases are separated and the solvents recovered utilizing any conventional separation process, such as distillation.
  • the solvent may be recovered from the two phases and recycled.
  • the extraction process is carried out at a temperature such that the feed and the solvent both remain substantially in the liquid phase.
  • the conditions are such that feed and solvent-water mixture are partially miscible.
  • the extraction temperature islimited by the boiling points of the constituents, and further limited by the critical solution temperatures of the feed and the solvent-water mixture. More particularly, it has been found that certain temperatures within the range thus provided are economically more attractive than others.
  • preferred extraction temperature ranges for the various solvent-water mixtures to be employed'in con; junction with this invention are from about 100 F. to about 250 F. It is noted that the temperature ranges em ployed are different for the different solvent-water mixtures. For the following solvent-water mixtures, the temperature ranges that may be employed are as follows:
  • the amount of solvent to be employed in conjunction with this invention may vary over a wide range. It is limited, at any given extraction temperature, by the and by the'solubility of the oil in the solvent system on the other and, in addition, by economic considerations. More particularly, it is preferred that the amount of total solvent utilized, i.e., NMP plus water, as shown by the treat or solvent-oil ratio, be between 50% and 1000%.
  • NMP will be employed as the selective solvent in combination with between 0.5 wt. percent and 20 Wt. percent water, based on total solvent, so as to raise the critical solution temperatures from between 50 F. and 550 F.
  • the temperatures to be employed forthe solvent-water mixtures in question are from F. to 250 F. At these conditions the actual number of gallons/hour of the solvent-water mixture and feed streams will'depend upon the scaleof the operation (i.e., commercial scale or pilot scale) and the particular size of the unit utilized but the'treat,'or solvent/oil ratio'employed, will be between 50% and 1000%, and from 1 to 20 stages may be utilized.
  • the feed stream consists of either lubricating oil fractions boiling within the range of 500 F. to 1100 F., containing between 5% and 70% aromatics, the aromatics ranging froin C to C 0r lube residua generally boiling about 900 F.
  • the two immiscible phases which are formed may be separated and the solvent in each phase recovered by any conventional means, such as distillation.
  • Example 1 V This example illustrates the method used to deter-mine the selectivity and solvent power of the NMP-Water mixtures herein disclosed.
  • Thirty m1. of waxy IO-grade Western Canadian-distillates of. diifering saturate/aromatic content were mixed with 30 ml. of the solvent in combination with dilfering amounts of water in a batch extractor at atmospheric pressure at a temperature about 100 to F. below the critical solution temperature of the particular solvent-water ratio and the distillate.
  • the rafiinate and extract phases were separated and the composition of each determined.
  • the refractive indices of the oil in each phase were determined; The refractive indices of the oil in each phase were determined as well as the dewaxed (pour point, 0 F.) viscosity index of the rafiinate oil.
  • a tertiary diagram for the solvent-oil system was thus constructed from these data according to the method of Hunter and Hash, Ind. & Eng. Chem., 27, 836 (1935,). The data are tabulated in Table II.
  • Example 2 To further illustrate the improved yield obtained with '6 only 54 volume percent of 90 viscosity index waxy product is obtained with a treat of 145 volume percent.
  • Example 3 To further illustrate the advantage of using N-methyl- 2-pyrrolidone in combination with water, a dewaxed 30- grade Western Canadian lube distillate was extracted in a crosscurrent fashion at 180 F. with aqueous N-methyl- 2-pyrrolidone containing 5% water by weight. It was found that approximately 6 crosscurrent treats of 100 volume percent each, based on the feed, were required to improve the viscosity index to 90 with a volume percent yield of 66. -By use of an established correlation between countercurrent and crosscurrent extractions the required countercurrent treat is 320 volume percent with a yield of 73 volume percent. If water is injected near the bottom of the extractor instead of premixed with N-methyl-2- pyrrolidone', the countercurrent treat is reduced to 180 volume percent with the same yield of 73 volume percent.
  • Example 4 The previous examples have illustrated the efliciency of NMP'and NMP/water as solvents relative to phenol and phenol/water for solvent extraction of lube oils.
  • Table IV The data are tabulated in Table IV.
  • a countercurrent extraction process for the upgrading of a hydrocarbon oil comprising contacting said oil with a solvent comprising Nemethyl-2-pyrrolidone and Water, in an extraction zone, thereby forming a solventoilmixture, said water and said N-methyl-2-pyrrolidone introduced separately into said extraction zone and wherein said water is introduced at a point below the point of introduction of said N-methyl-Z-pyrrolidone, so as to prevent substantial mixing of said water and said N-methyl-Z-pyfrolidone prior tosaid N-methyl-2-pyrrolidone contacting said oil.
  • oil selected from the group. consisting of petroleum distillate fractions and lube residua', said process comprising contacting said oil with N-methyl-Z-pyrrolidone and between about 0.5 wt. p e rcent and about 30 wt. percent water based on total solvent, inian extraction zone, thereby forming an extract phase and "a ralfinate phase, said waterand said N-methyl-Z-pyrrolidone introduced separately into said-extraction zone and wherein said 'water is introduced at a point below-the point.

Landscapes

  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00234733A 1972-03-15 1972-03-15 Countercurrent lube extraction with dual solvent system Expired - Lifetime US3843515A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US00234733A US3843515A (en) 1972-03-15 1972-03-15 Countercurrent lube extraction with dual solvent system
CA146,957A CA978125A (en) 1972-03-15 1972-07-12 Countercurrent lube extraction with dual solvent system
DE2235454A DE2235454C2 (de) 1972-03-15 1972-07-20 Gegenstromextraktionsverfahren zur Abtrennung der aromatischen Bestandteile aus einem Kohlenwasserstofföl mit N-Methyl-2-Pyrrolidon und Wasser
IT27509/72A IT963440B (it) 1972-03-15 1972-07-27 Estrazione di olio lubrificante in controcorrente usando un sistema a due solventi
FR7232603A FR2175722B1 (de) 1972-03-15 1972-09-14
JP9310572A JPS568079B2 (de) 1972-03-15 1972-09-16

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00234733A US3843515A (en) 1972-03-15 1972-03-15 Countercurrent lube extraction with dual solvent system

Publications (1)

Publication Number Publication Date
US3843515A true US3843515A (en) 1974-10-22

Family

ID=22882571

Family Applications (1)

Application Number Title Priority Date Filing Date
US00234733A Expired - Lifetime US3843515A (en) 1972-03-15 1972-03-15 Countercurrent lube extraction with dual solvent system

Country Status (6)

Country Link
US (1) US3843515A (de)
JP (1) JPS568079B2 (de)
CA (1) CA978125A (de)
DE (1) DE2235454C2 (de)
FR (1) FR2175722B1 (de)
IT (1) IT963440B (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4168226A (en) * 1977-04-08 1979-09-18 Exxon Research & Engineering Co. Thermal stabilization of N-methyl-2-pyrrolidone
US4396492A (en) * 1981-11-03 1983-08-02 Exxon Research And Engineering Co. Method for retarding corrosion in petroleum processing operation using N-methyl pyrrolidone
US4604184A (en) * 1983-11-16 1986-08-05 Domtar Inc. Modified coal-tar pitch
US5120900A (en) * 1990-12-05 1992-06-09 Exxon Research And Engineering Company Integrated solvent extraction/membrane extraction with retentate recycle for improved raffinate yield
US5616238A (en) * 1994-05-20 1997-04-01 Exxon Research And Engineering Company Solvent extraction of hydrocarbon oils producing an increased yield of improved quality raffinate
WO2001042395A1 (en) * 1999-12-10 2001-06-14 Exxonmobil Research And Engineering Company Process for solvent extraction of hydrocarbons providing an increased yield of raffinate
US20060086664A1 (en) * 2003-12-19 2006-04-27 Wills Robert A System for liquid extraction, and methods
US20060124544A1 (en) * 2002-12-19 2006-06-15 Karges-Faulconbridge, Inc. System for liquid extraction, and methods
WO2011081601A1 (en) * 2009-12-30 2011-07-07 Irpc Public Company Limited Methods and processes for producing process oils with a low polyaromatic hydrocarbon content

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53129802U (de) * 1977-12-19 1978-10-14

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE630077A (de) *
US2246297A (en) * 1938-12-10 1941-06-17 Standard Oil Dev Co Solvent extraction process
CA944301A (en) * 1969-03-11 1974-03-26 Charles C. Hong Lube extraction with dual solvent systems

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4168226A (en) * 1977-04-08 1979-09-18 Exxon Research & Engineering Co. Thermal stabilization of N-methyl-2-pyrrolidone
US4396492A (en) * 1981-11-03 1983-08-02 Exxon Research And Engineering Co. Method for retarding corrosion in petroleum processing operation using N-methyl pyrrolidone
US4604184A (en) * 1983-11-16 1986-08-05 Domtar Inc. Modified coal-tar pitch
US5120900A (en) * 1990-12-05 1992-06-09 Exxon Research And Engineering Company Integrated solvent extraction/membrane extraction with retentate recycle for improved raffinate yield
US5616238A (en) * 1994-05-20 1997-04-01 Exxon Research And Engineering Company Solvent extraction of hydrocarbon oils producing an increased yield of improved quality raffinate
EP1250399A4 (de) * 1999-12-10 2004-03-17 Exxonmobil Res & Eng Co Verfahren zur solventextraktion von kohlenwasserstoffen zur erzielung eines erhöhten wirkungsgrades von raffinaten
US6294082B1 (en) * 1999-12-10 2001-09-25 Exxon Research And Engineering Company Process for solvent extraction of hydrocarbons providing an increased yield of raffinate
EP1250399A1 (de) * 1999-12-10 2002-10-23 Exxon Research and Engineering Company Verfahren zur solventextraktion von kohlenwasserstoffen zur erzielung eines erhöhten wirkungsgrades von raffinaten
WO2001042395A1 (en) * 1999-12-10 2001-06-14 Exxonmobil Research And Engineering Company Process for solvent extraction of hydrocarbons providing an increased yield of raffinate
US20060124544A1 (en) * 2002-12-19 2006-06-15 Karges-Faulconbridge, Inc. System for liquid extraction, and methods
US20100307021A1 (en) * 2002-12-19 2010-12-09 KFI Intellectual Properties LLC. System for liquid extraction, and methods
US7857975B2 (en) 2002-12-19 2010-12-28 Kfi Intellectual Properties, L.L.C. System for liquid extraction, and methods
US20110088277A1 (en) * 2002-12-19 2011-04-21 Kfi Intellectual Properties L.L.C. System for liquid extraction, and methods
US8323500B2 (en) 2002-12-19 2012-12-04 Kfi Intellectual Properties, L.L.C. System for liquid extraction, and methods
US8336226B2 (en) 2002-12-19 2012-12-25 Kfi Intellectual Properties, L.L.C. System for liquid extraction, and methods
US20060086664A1 (en) * 2003-12-19 2006-04-27 Wills Robert A System for liquid extraction, and methods
US7776218B2 (en) 2003-12-19 2010-08-17 Kfi Intellectual Properties L.L.C. System for liquid extraction, and methods
WO2011081601A1 (en) * 2009-12-30 2011-07-07 Irpc Public Company Limited Methods and processes for producing process oils with a low polyaromatic hydrocarbon content

Also Published As

Publication number Publication date
DE2235454C2 (de) 1983-10-13
JPS568079B2 (de) 1981-02-21
JPS493906A (de) 1974-01-14
CA978125A (en) 1975-11-18
FR2175722A1 (de) 1973-10-26
DE2235454A1 (de) 1973-09-20
IT963440B (it) 1974-01-10
FR2175722B1 (de) 1976-10-29

Similar Documents

Publication Publication Date Title
US2162963A (en) Process for desulphurizing mineral oils
US4125458A (en) Simultaneous deasphalting-extraction process
US4781820A (en) Aromatic extraction process using mixed polyalkylene glycols/glycol ether solvents
US2114524A (en) Extraction process
US5039399A (en) Solvent extraction of lubricating oils
US4013549A (en) Lube extraction with NMP/phenol/water mixtures
US3843515A (en) Countercurrent lube extraction with dual solvent system
US2662843A (en) Shale oil refining
US2086487A (en) Solvent extraction
US3249532A (en) Solvent extraction of aromatics
US2396303A (en) Refining hydrocarbon oils
US2520006A (en) Vapor liquid solvent extraction process
US2138833A (en) Process for extracting oils
US3291718A (en) Combination lube process
US5616238A (en) Solvent extraction of hydrocarbon oils producing an increased yield of improved quality raffinate
US4333824A (en) Refining highly aromatic lube oil stocks
US2307242A (en) Solvent treating of mineral oils
US3322667A (en) Hydrocarbon stripping process
CA1262366A (en) Extraction of aromatics with ethyl acetoacetate
US2402799A (en) Separation of sulphur and aromatic compounds from oil
US2534382A (en) Method of refining oil with a solvent
US2288853A (en) Hydrocarbon oil treatment
US2717229A (en) Solvent extraction process
US2041308A (en) Refining mineral oil
US2389176A (en) Production of aviation gasoline