US2069329A - Process of refining oils - Google Patents

Process of refining oils Download PDF

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Publication number
US2069329A
US2069329A US12008A US1200835A US2069329A US 2069329 A US2069329 A US 2069329A US 12008 A US12008 A US 12008A US 1200835 A US1200835 A US 1200835A US 2069329 A US2069329 A US 2069329A
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US
United States
Prior art keywords
solvent
hydrocarbons
sulfur compounds
mixture
distillation
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
US12008A
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English (en)
Inventor
Roelfsema Petrus Jurjen
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.)
Shell Development Co
Original Assignee
Shell Development Co
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Filing date
Publication date
Application filed by Shell Development Co filed Critical Shell Development Co
Priority to US12008A priority Critical patent/US2069329A/en
Priority to GB8031/36A priority patent/GB462630A/en
Priority to NL77051A priority patent/NL43587C/xx
Priority to FR804488D priority patent/FR804488A/fr
Priority to US95385A priority patent/US2114852A/en
Application granted granted Critical
Publication of US2069329A publication Critical patent/US2069329A/en
Priority to FR824157D priority patent/FR824157A/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/40—Extractive distillation
    • 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
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/09—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acid salts
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/08—Azeotropic or extractive distillation

Definitions

  • This invention relates to the treating of hydrocarbon products and is particularly concerned with a process for removing sulfur compounds from hydrocarbon oils such as gasoline, kerosene,
  • naphthas solar oils, fuel oils, etc.
  • which may be either straight run distillates or crackeddistillates, and may be derived from petroleum crudes, fractions of coal tar, or-brown coal tar, and mixtures obtained by the hydrogenation of carbonaceous substances.
  • myprocess may be operated more efciently, i; e., so as to improve the purity of the sulfur compounds which are ob-v tained in the bottom product, by fractionating in I the manner disclosed in my copending application Serial No. 12,007 filed March 20, 1935.
  • the ratio of desirable hydrocarbons to the solvent in the top product is maintained equal to the ratio of .these substances in the feed. This may be effected according to either of the following modes of operation: 40
  • a. 'Ihe overhead mixture, or a portion thereof, is treated to withdraw therefrom a top product containing the solvent and the hydrocarbons in the same ratio as they occur in the feed, and the l remaining portion of the overhead mixture is re- A turned to the column, either with the reiiux, or separately at another level in the column.
  • a convenient method of withdrawing this top product from the overhead mixture consists in chilling the portion of the overhead which is ⁇ to be treated so as to cause it to stratify into two liquid phases of different composition, i.
  • the ratio of the solvent and the initial sulfur-bearing hydrocarbon mixture is so controlled as to produce a feed composition which contains the solventv and the hydrocarbons in the same ratio as they occur in the overhead mixture, which is then withdrawn from the system as top product.
  • Another purpose of this preliminary distillation is to effect an increased efficiency of the process of ,my invention.
  • I have found that if the fractions treated having boiling ranges which are not substantially greater than 30 C. or 80 C., I am, in some cases, able to obtain a much sharper separation, whereby both the quantity of sulfur compounds in the distillate and the quantity of hydrocarbons in the bottom product are greatly reduced.
  • a solvent having a boiling point which is sufllciently lovr to cause a mixture of said solvent and the highest boiling. hydrocarbon of the mixture to boil at a temperature below the lowest boiling sulfur compounds to be removed. It is, therefore, possible to use solvents boiling at temperatures below the boiling range of the fraction, or at temperatures falling within or even above the said range, provided that the solvent and the hydrocarbons form low boiling mixtures which boil below the lowest boiling sulfur compound, or sufficiently low to produce aflnal product of a desired sulfur content. While my process may be employed to cause the removal of substantially all of the sulfur, it is alsopracticcd when the sulfur content is merely lowered and a portion of the sulfur is retained in the final product.
  • I may employ any solvent which has the above described boiling temperature characteristics, and which is a selectivo solvent for the sulfur compounds.
  • I may use organic polar liquids of the type used in the liquid solvent extraction of hydrocarbon mixtures to cilecta separation between aromatic and paraillnic hydrocarbons, or
  • R designates an alkyl radical, which may be either alphyl or aryl.
  • solvents are: Nitrobenzene, benzonitrile, monochloracetontrile, phenyl thiocyanate,4 phenolthiocyanate, formate of pyridine, benzaldehyde, acetone, furi'ural, furfuryl alcohol, chlorisopropyl alcohol, diacetone alcohol, aniline methyl lactate, triacetin, diacetin, methyl nitrobenzoate,
  • My invention is not, however, limited to the specic solvents enumerated, nor to solvents containing the enumerated chemical groups, but may be used with any selective solvent for sulfur compounds.
  • My invention is not concerned with distillation processes employing immiscible liquids, like water,and described Ain the British Specication No. 365,571.
  • I is a fractional distillation column, provided with an intake manifold 2,
  • a valve 'I may beprovided to regulate the quantity of reux, and may, if desired, be operated automatically, as by a'fiow controller, a thermostat or a pressure responsive devicelocated in the fractionating column I.
  • the top product may be withdrawn at 6 from condensate of the condenser 4, or a separate top product takeoff may be provided. Heaters, heat exchangers, pumps, gauges, and other auxiliary equipment, not shown, may be provided.
  • a feed mixture of hydrocarbons and sulfur compounds iiows through a conduit 3 and valve I0, and is mixed in a mixing device II with a suitable selective solvent introduced from a storage I2 through a conduit I3 and valve I4, and
  • fractionating column I A portionof the condensate from the condenser 4, consisting of hydrocarbons containing no sulfur or substantially reduced amounts of sulfur, andsolvent, is withdrawn through 6 as top product Aat the proper rate, controlled by 'a valve I5.
  • the solvent may in certain cases be allowed to remain in the top product, as when it imparts desirable characteristics to the hydrocarbons. If'desired, the
  • solvent may be recovered by feeding the top product into a fractional distillation column I8, which may besimilar to the column I, in that it is equipped with an intake manifold I1, an overhead takeoif I8, a reflux condenser. I9, ⁇ and a reflux line 20; controlled by a valve 2
  • the solvent in any desired state of purity. may be withdrawn at 22 and returned tostorage through a. conduit 23, and the hydrocarbons may be recovered at 24 at a rate controlled by a valve 25.
  • the sulfur compounds may be withdrawn at 2'6 in a. concentrated form as a bottom product of the column I, at a rate controlled by a valve 21.
  • the quantity of these sulfur compounds is generally very small as compared to the quantity of hydrocarbons distilled, and I have found it to be desirable, but not necessary, to permit the sulfur compounds toy accumulate in the bottom of. the still, which may be operated either continuously or in a batch operation, and to remove the bottom product only after a sufficient amount of sulfur l compounds has been concentrated to permit the removal as bottoms of a product which is rich in sulfur compounds, and low in hydrocarbons, thereby materially reducing the loss of the desired hydrocarbons.
  • I may initially close the valve 21 and operate the column I until enoughv l example, at the same rate as the sulfur compounds are fed into the column at 2.
  • I may initiallyrun a number of batches and then remove all of the bottoms at once, or may then withdraw after each run only as much sulfur bottoms as was introduced during the preceding run. Similarly, in continuous operations, I may initially operate for the time required to build up the desired sulfur concentration, and then either remove all of the bottoms, Aor open the valve 21 so as to withdraw a small quantity sufficient to maintain a substantially constant sulfur concentration in the column.
  • the bottom product from 26 may, if desired, be further fractionated to recover the solvent, if it is present in sufficient quantity to warrant recovery.
  • I l may reduce the load on the fractionator -I6 by rst cooling and/or chilling the top product in a cooler 28, and feeding it through a conduit 29 into a decanter, centrifuge, or other suitable phase separator 33, valve 3
  • the cooler 28 cools the top product to a temperature at which it separates into two liquid phases. Assuming that the phase consisting mainly or totally of the solvent is heavier than the other phase, it is withdrawn at 32, and may be returned to storage through a conduit 23', r taken off at 33 as a separate product. It may be, if desired, further concentrated by any desired method, such as distillation, salting out, extraction, etc., before being returned to the storage I2. phase, which is richer in hydrocarbons, may be withdrawn at 34 and taken off as a product at 35, or fed to the fractionating column I6 through a conduit 36.
  • the sep-V arated phases from "the phase separator 30 can be divided into a top product of the desired com- Y position and quantity, which is withdrawn through the conduits 38 and 39, and, valves 45 and 46 being open, a secondary or added reflux, which is returned to the column I through conduits 40 and '4I and introduced either with the main reflux, for instance, after being mixed therewith in a mixer
  • the other vent but may have a composition corresponding to that of the phase withdrawn at 32 and returned through the conduit 23.
  • an overhead mixture will be withdrawn at 3 which will contain hydrocarbons and the solvent in a ratio Y, which will not, save.
  • valve 1 it is possible to close valve 1, and to carry all of the reflux through conduits lil and Il.
  • the valves I and il are adjusted so that X, the ratio of hydrocarbons to solvent in the feed at 2 is equal to Y, the ratio of these components in the overhead mixture.
  • the valves 45 and 46 remain closed and the top product composition is the same as that of the overhead mixture.
  • the top product may, therefore, be fed directly into the column I6 through the valve I5, thereby eliminating the phase separator 3l.
  • the. phase separator 30 may be employed to effect the separation of the solvent and the hydrocarbons in the manner described above.
  • the hydrocarbons which are useful in my distillation are preferential solvents for certain components of hydrocarbon oils
  • the hydrocarbons may be separated into portions which are relatively more parafiinic and less paraiiinic.
  • the hydrocarbons withdrawn at 34 are more parafiinic than those which occur inv the solvent-phase which is withdrawn at 32. It is often possible to further extract the phase flowing through conduit 39 with additional solvent from the tank l2 or with a different solvent, to
  • a continuous process of refining a hydrocarbon fraction containing sulfur compounds the steps of continuously introducing the said fraction and a preferential solvent for the said sulfur compounds into a distilling apparatus, maintaining within the apparatus counterow.- ing streams of vapors and reflux derived from the combined mixture, maintaining the conditions of temperature, pressure, and reflux in said apparatus to distill at least a substantial portion of the solvent together with refined hydrocarbons, continuously withdrawing from the apparatus a top product containing the refined hydrocarbons and forming a distillation bottom product inwhich sulfur compounds are concentrated.
  • the process of refining a hydrocarbon fraction containing sulfur compounds which comprises introducing a feed mixture containing the said fraction and a preferential solvent for the said sulfur compounds into a distillation zone, maintaining the conditions of temperature and pressure in said zone to distill at least a sub" stantial portion of the solvent together with refined hydrocarbons, withdrawing ffrom the distillation zone a rectified overhead mixture derived from the said feed mixture forming a distillation bottom product in which sulfur compounds are concentrated, withdrawing a portion of the said overhead mixture as a top product and adjusting the quantity of the solvent in A the feed mixture so that the solvent and the hydrocarbons occur in the feed in substantially the same ratio as they occur in the top product.
  • the process of ren'ning a hydrocarbon fraction containing sulfur ⁇ compounds which comprises introducing a feed mixture containing the said fraction and a preferential solvent for the said sulfur compounds into a distillation zone, maintaining the conditions of temperature and pressure in said zone to distill at least a substantial portion of the solvent together-with reiined hydrocarbons, withdrawing from the distillation zone a rectified overhead mixture derived from the said feed mixture forming a distillation bottom product in which sulfur compounds are concentrated, condensing and cooling at leasta portion of the said overhead mixture to cause it to separate into two liquid phases withdrawing from the said phases a top product containing the solvent and the hydrocarbons in a ratio which is not substantially greater than the ratio in which they occur in the said feed mixture, and returning to the distillation zone the withdrawn overhead mixture less the withdrawn top product.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (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)
US12008A 1935-03-20 1935-03-20 Process of refining oils Expired - Lifetime US2069329A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US12008A US2069329A (en) 1935-03-20 1935-03-20 Process of refining oils
GB8031/36A GB462630A (en) 1935-03-20 1936-03-17 A process of refining hydrocarbon oils
NL77051A NL43587C (sv) 1935-03-20 1936-03-19
FR804488D FR804488A (fr) 1935-03-20 1936-03-20 Procédé de raffinage des huiles
US95385A US2114852A (en) 1935-03-20 1936-08-11 Process for desulphurizing mineral oil distillates
FR824157D FR824157A (fr) 1935-03-20 1937-07-09 Procédé pour la désulfuration des distillats d'huile minérale

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12008A US2069329A (en) 1935-03-20 1935-03-20 Process of refining oils
US95385A US2114852A (en) 1935-03-20 1936-08-11 Process for desulphurizing mineral oil distillates

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US2069329A true US2069329A (en) 1937-02-02

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US95385A Expired - Lifetime US2114852A (en) 1935-03-20 1936-08-11 Process for desulphurizing mineral oil distillates

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US95385A Expired - Lifetime US2114852A (en) 1935-03-20 1936-08-11 Process for desulphurizing mineral oil distillates

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US (2) US2069329A (sv)
FR (2) FR804488A (sv)
GB (1) GB462630A (sv)
NL (1) NL43587C (sv)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2427988A (en) * 1945-04-24 1947-09-23 Carnegie Illinois Steel Corp Process for removing sulphur compounds from hydrocarbons
US2428611A (en) * 1941-11-17 1947-10-07 Union Oil Co Recovery of azeotrope former in azeotropic distillation of hydrocarbons
US2522752A (en) * 1945-02-17 1950-09-19 Union Oil Co Thiophene acylation with catalyst of sulfuric acid-carboxylic acid complex
US2636883A (en) * 1945-01-31 1953-04-28 Union Oil Co Thienyl ketones
US2666794A (en) * 1951-06-08 1954-01-19 Phillips Petroleum Co Desulfurization of hydrocarbons by extraction with phenylacetonitrile
US2671047A (en) * 1951-09-29 1954-03-02 Standard Oil Co Refining hydrocarbon materials with so2 and bf3
US2852436A (en) * 1955-03-28 1958-09-16 Gulf Research Development Co Process for removal of elemental sulfur from crude petroleum oils with an aliphatic diamine and an adsorbent
US4455221A (en) * 1983-02-09 1984-06-19 Intevep Process for upgrading heavy hydrocarbons employing a diluent
US4776927A (en) * 1986-01-25 1988-10-11 Krupp=Koppers Gmbh Process for the separation of aromatic hydrocarbons from a hydrocarbon mixture
US4909925A (en) * 1986-01-30 1990-03-20 The British Petroleum Company P.L.C. Removal of hydrogen sulphides
US6802959B1 (en) * 2000-06-23 2004-10-12 Conocophillips Company Separation of olefinic hydrocarbons from sulfur-containing hydrocarbons by use of a solvent
CN103965078A (zh) * 2014-05-05 2014-08-06 大连理工大学 一种脱酚酚油制苯甲腈和清洁燃料的方法

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE747402C (de) * 1941-09-26 1944-09-27 Edeleanu Gmbh Verfahren zur Gewinnung von oelfreiem Paraffin aus Teeren bzw. Teerdestillaten
US2433751A (en) * 1943-09-30 1947-12-30 Universal Oil Prod Co Separation of organic compounds
US2422341A (en) * 1944-12-26 1947-06-17 Phillips Petroleum Co Solvent extraction
US2567174A (en) * 1949-01-24 1951-09-11 Standard Oil Dev Co Process for improving stability and engine cleanliness characteristics of petroleum fractions
US2662843A (en) * 1951-05-25 1953-12-15 Shell Dev Shale oil refining
US2698278A (en) * 1952-06-20 1954-12-28 Socony Vacuum Oil Co Inc Solvent extraction
US2813918A (en) * 1953-06-05 1957-11-19 Phillips Petroleum Co Solvent extraction with the operation of the uppermost portion of the extractor as a vapor liquid fractionation zone
DE1117249B (de) * 1959-03-13 1961-11-16 Dr Georg Kowalski Verfahren zur Extraktion von Mineraloelen durch Behandlung mit Nitrilen
FR1302375A (fr) * 1960-10-05 1962-08-31 Houilleres Bassin Du Nord Procédé de raffinage d'hydrocarbures aromatiques
NL276254A (sv) * 1961-03-25
US3205164A (en) * 1962-09-24 1965-09-07 Universal Oil Prod Co Hydrogen sulfide removal
US3424673A (en) * 1966-03-07 1969-01-28 Sun Oil Co Process for hydrodesulfurizing the lower boiling fraction of a cracked gas oil blend
US3919402A (en) * 1973-08-06 1975-11-11 Kvb Inc Petroleum oil desulfurization process
US3957625A (en) * 1975-02-07 1976-05-18 Mobil Oil Corporation Method for reducing the sulfur level of gasoline product
US4485007A (en) * 1982-06-15 1984-11-27 Environmental Research And Technology Inc. Process for purifying hydrocarbonaceous oils
US5599441A (en) * 1995-05-31 1997-02-04 Mobil Oil Corporation Alkylation process for desulfurization of gasoline
US20130186805A1 (en) 2011-07-29 2013-07-25 Omer Refa Koseoglu Selective middle distillate hydrotreating process

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2428611A (en) * 1941-11-17 1947-10-07 Union Oil Co Recovery of azeotrope former in azeotropic distillation of hydrocarbons
US2636883A (en) * 1945-01-31 1953-04-28 Union Oil Co Thienyl ketones
US2522752A (en) * 1945-02-17 1950-09-19 Union Oil Co Thiophene acylation with catalyst of sulfuric acid-carboxylic acid complex
US2427988A (en) * 1945-04-24 1947-09-23 Carnegie Illinois Steel Corp Process for removing sulphur compounds from hydrocarbons
US2666794A (en) * 1951-06-08 1954-01-19 Phillips Petroleum Co Desulfurization of hydrocarbons by extraction with phenylacetonitrile
US2671047A (en) * 1951-09-29 1954-03-02 Standard Oil Co Refining hydrocarbon materials with so2 and bf3
US2852436A (en) * 1955-03-28 1958-09-16 Gulf Research Development Co Process for removal of elemental sulfur from crude petroleum oils with an aliphatic diamine and an adsorbent
US4455221A (en) * 1983-02-09 1984-06-19 Intevep Process for upgrading heavy hydrocarbons employing a diluent
US4776927A (en) * 1986-01-25 1988-10-11 Krupp=Koppers Gmbh Process for the separation of aromatic hydrocarbons from a hydrocarbon mixture
US4909925A (en) * 1986-01-30 1990-03-20 The British Petroleum Company P.L.C. Removal of hydrogen sulphides
US6802959B1 (en) * 2000-06-23 2004-10-12 Conocophillips Company Separation of olefinic hydrocarbons from sulfur-containing hydrocarbons by use of a solvent
CN103965078A (zh) * 2014-05-05 2014-08-06 大连理工大学 一种脱酚酚油制苯甲腈和清洁燃料的方法

Also Published As

Publication number Publication date
FR804488A (fr) 1936-10-24
FR824157A (fr) 1938-02-02
NL43587C (sv) 1938-07-15
GB462630A (en) 1937-03-12
US2114852A (en) 1938-04-19

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