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US2789999A - Treatment of naphthenic acids - Google Patents

Treatment of naphthenic acids Download PDF

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Publication number
US2789999A
US2789999A US447674A US44767454A US2789999A US 2789999 A US2789999 A US 2789999A US 447674 A US447674 A US 447674A US 44767454 A US44767454 A US 44767454A US 2789999 A US2789999 A US 2789999A
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Prior art keywords
naphthenic acids
metal
contact
treatment
particulate
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US447674A
Inventor
James L Jezl
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Sunoco Inc
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Sun Oil Co
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Classifications

    • 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
    • C10G19/00Refining hydrocarbon oils in the absence of hydrogen, by alkaline 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06Metal salts, or metal salts deposited on a carrier
    • 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
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203Naphthenic acids, TAN
    • 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
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/205Metal content

Definitions

  • This invention relates to the treatment of naphthenic acids, to improve the color stability thereof.
  • naphthenic acids are subjected to contact treatment with particulate range ofabout 60 F. to 500 F.
  • the .contact'treatment may be carried out by procedures such as contact filtration or percolation, or the contact may be efiected simply by storing the naphthenic acids in admixture with the particulate metal.
  • the temperature of the treatment of the invention is dependent to a large extent upon the manner in which the contact is conducted.
  • temperatures in the range of about 60 F. to 200 F. are suitable. These lower temperatures are preferred since prolonged high temperature is detrimental to naphthenic acid color and might lessen the stability improvement effected through the treatment of the invention.
  • suitable temperatures normally are in the range of about 200 F. to 500 F.
  • the temperature should be sufficiently low to avoid appreciable formation of aluminum naphthenate, while high enough to insure adequate color stabilizing activity of the particulate metal at short contact times.
  • a temperature of from 300 F. to 400 F. is preferred for a contact treatment of relatively short duration such as a percolation contact.
  • the naphthenic acids treated according to this invention are preferred de-oiled vacuum distilled acids, although crude naphthenic acids i. e. containing less than 50% by weight of oil, may be treated with advantage by this invention.
  • the naphthenic acids are treated directly after vacuum distillation such as by passing the distillate naphthenic acids, prior to cooling, through a bed of particulate metal.
  • the thusly treated acids may then be cooled and stored.
  • An alternative preferred practice comprises storing the distillate naphthenic acids in vessels which contain substantial quantities of particulate aluminum or magnesium. These acids may be subjected to filtration upon transfer from the storage vessels and thus be separated from the particulate metal.
  • the relative amounts of naphthenic acids and particulate metal as well as the time of contact are dependent upon the stability improvement desired and upon the particular mode of contact employed. Normally, greater relative United States Patent metallic aluminum or magnesium at temperatures in the "ice 2 amounts of particulate metal and longer contact times favor increased color stability improvement- In the practice ofthis invention whereby naphthenic acids are stored in admixture with particulate aluminum or magnesium, an amount of the metal equal to about 0.5% to by weight of the naphthenic acids is generally suitable to give substantial color stability improvement, although amounts of particulate metal outside the above range may advantageously be utilized on occasion.
  • naphthenic acid liquid hourly space velocities in the range of about 0.5 to l0volumes of liquid feed per volume of particulate metal per hour are normally suitable to insure substantial naphthenic acid color stability improvement. Some improvement will result even from a very brief contact, however, and liquid hourly space velocities outside the above range may be used to ad vantage on occasion. Care must be exercised that the percolation contact is not unduly prolonged at higher temperatures since the color stability improvement may be lessened by the detrimental elfect of prolonged high temperatures on naphthenic acid color.
  • the particle size of the particulate metals used in this invention is important in order to insure a uniform, active contact between the naphthenic acids and the metal. In general, smaller sized particles result in greater color stability improvement per weight of metal used due to the larger contact surface area of the smaller particles. However, there are otherfactors which affect the particle size of the metal. Consideration must be given to the particular method by which the fluid-metal contact is carried out. Granular metal is preferred for use in the fixed bedor percolation contact. The metal particles must be of sulficient size as to be readily retainable betWeen obstructions which permit the passage therethrough of liquid, while at the same time the metal particles should be small to insure an effective color stabilizing contact. Normally, metal particles having a particle size of about 16 to 60 mesh (Tyler standard screen) are preferable in the percolation contact treatment of this invention although somewhat larger metal chips or turnings may be used with reduced contact effectiveness.
  • An alternate method comprises filling the storage vessel with sufficient larger sized metal particles to insure uniform fluid-metal contact.
  • larger sized metal particles as for example metal chips or turnings may be used, but a greater weight of metal is required to insure affective contact than with the smaller particles described above.
  • De-oiled vacuum distilled naphthenic acids having an acid no. of about 178 mg. of KOH per gram and an SSU viscosity at 210 F. of about 106 were divided into three portions. The first portion was admixed with 1% by Weight of powdered aluminum, and the second portion with 1% by Weight of powdered magnesium. The third portion was not treated with these metals. All three samples were aged at 250 F. for 24 hours in contact with From these tabulated results it may be seen that both aluminum and magnesium are effective in improving naphthenic acid color stability. The improvement through theuse of aluminum was somewhat greater than that occasioned through the use of magnesium.
  • the method for improving the color stability of naphthenic acids which consists of contacting-naphthenic acids with treating agent consisting essentially of particulate metal selected from the group consisting of aluminum and magnesium at a temperature in the range of 60 F. to 500 F.
  • the method for improving the color stability of naphthenic acids which comprises: storing naphthenic acids in admixture with treating agent consisting essential- -ly of particulate metal selected fromthe group-consisting of aluminum and magnesium at a temperature in th range of F. to 200 F.
  • the method for improving the color stability of naphthenic acids which consists of passing naphthenic acids through a bed of treating agent consisting essentially of particulate metal selected from the group consisting of aluminum and magnesium at a temperature in the range of 200 F. to 500 F.
  • the method for improving the color stability of naphthenic acids which comprises: storing naphthenic acids at a temperature in the range of 60 F. to 200 F. in admixture with treating agent consisting essentially of particulate metal selected from the group consisting of aluminum and magnesium, said metal having a particle size of -400 mesh (Tyler standard screen).

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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)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

TREATMENT OF NAPHTHENIC ACIDS James L. Jezl, Swarthmore, Pa., assignor to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey No Drawing. Application August 3, 1954,
'Serial No. 447,674
7 Claims. (Cl. 260-514) This invention relates to the treatment of naphthenic acids, to improve the color stability thereof.
vacuum distillation, but the light colored acids are not color stable and tend to darken rapidly in storage.
In accordance with the present invention, naphthenic acids are subjected to contact treatment with particulate range ofabout 60 F. to 500 F. The .contact'treatment may be carried out by procedures such as contact filtration or percolation, or the contact may be efiected simply by storing the naphthenic acids in admixture with the particulate metal. I have made the surprising discovery that naphthenic acids are substantially improved in color stability by the contact treatment of this invention.
The temperature of the treatment of the invention is dependent to a large extent upon the manner in which the contact is conducted. In general for prolonged contact treatments as when naphthenic acids are stored in admixture with particulate aluminum or magnesium, temperatures in the range of about 60 F. to 200 F. are suitable. These lower temperatures are preferred since prolonged high temperature is detrimental to naphthenic acid color and might lessen the stability improvement effected through the treatment of the invention. For relatively short contact times such as during percolation treatment, somewhat higher temperatures are preferred; suitable temperatures normally are in the range of about 200 F. to 500 F. The temperature should be sufficiently low to avoid appreciable formation of aluminum naphthenate, while high enough to insure adequate color stabilizing activity of the particulate metal at short contact times. Generally a temperature of from 300 F. to 400 F. is preferred for a contact treatment of relatively short duration such as a percolation contact.
The naphthenic acids treated according to this invention are preferred de-oiled vacuum distilled acids, although crude naphthenic acids i. e. containing less than 50% by weight of oil, may be treated with advantage by this invention.
In a preferred practice, the naphthenic acids are treated directly after vacuum distillation such as by passing the distillate naphthenic acids, prior to cooling, through a bed of particulate metal. The thusly treated acids may then be cooled and stored. An alternative preferred practice comprises storing the distillate naphthenic acids in vessels which contain substantial quantities of particulate aluminum or magnesium. These acids may be subjected to filtration upon transfer from the storage vessels and thus be separated from the particulate metal.
The relative amounts of naphthenic acids and particulate metal as well as the time of contact are dependent upon the stability improvement desired and upon the particular mode of contact employed. Normally, greater relative United States Patent metallic aluminum or magnesium at temperatures in the "ice 2 amounts of particulate metal and longer contact times favor increased color stability improvement- In the practice ofthis invention whereby naphthenic acids are stored in admixture with particulate aluminum or magnesium, an amount of the metal equal to about 0.5% to by weight of the naphthenic acids is generally suitable to give substantial color stability improvement, although amounts of particulate metal outside the above range may advantageously be utilized on occasion.
When the contact treatment comprises percolating naphthenic acids through a bed of particulate aluminum or magnesium, naphthenic acid liquid hourly space velocities in the range of about 0.5 to l0volumes of liquid feed per volume of particulate metal per hour are normally suitable to insure substantial naphthenic acid color stability improvement. Some improvement will result even from a very brief contact, however, and liquid hourly space velocities outside the above range may be used to ad vantage on occasion. Care must be exercised that the percolation contact is not unduly prolonged at higher temperatures since the color stability improvement may be lessened by the detrimental elfect of prolonged high temperatures on naphthenic acid color.
The particle size of the particulate metals used in this invention is important in order to insure a uniform, active contact between the naphthenic acids and the metal. In general, smaller sized particles result in greater color stability improvement per weight of metal used due to the larger contact surface area of the smaller particles. However, there are otherfactors which affect the particle size of the metal. Consideration must be given to the particular method by which the fluid-metal contact is carried out. Granular metal is preferred for use in the fixed bedor percolation contact. The metal particles must be of sulficient size as to be readily retainable betWeen obstructions which permit the passage therethrough of liquid, while at the same time the metal particles should be small to insure an effective color stabilizing contact. Normally, metal particles having a particle size of about 16 to 60 mesh (Tyler standard screen) are preferable in the percolation contact treatment of this invention although somewhat larger metal chips or turnings may be used with reduced contact effectiveness.
In the contact treatment of the invention wherein naphthenic acids are stored in admixture with particulate aluminum or magnesium, additional factors must be considered in selecting a suitable metal particle size. For best results there must be a continuous intimate contact between the stored naphthenic acids and the particulate metal. This may be accomplished with lesser amounts of metal by regulating the metal particle size such that the metal remains dispersed throughout the stored acids as a suspension for a substantial length of time. Metal particles having a particle size of about 100-400 mesh (Tyler standard screen) are preferred for this type of treatment. Somewhat larger particles may be used if means are supplied whereby the stored acids are agitated.
An alternate method comprises filling the storage vessel with sufficient larger sized metal particles to insure uniform fluid-metal contact. In this latter case, larger sized metal particles as for example metal chips or turnings may be used, but a greater weight of metal is required to insure affective contact than with the smaller particles described above.
The exact nature of the color stabilizing reaction between the particulate magnesium or aluminum and the naphthenic acids is not definitely known at this time. It is, however, thought that compounds which are deleterious to naphthenic acid color stability are neutralized or reduced, or are in some way saturated and deactivated by contact with the particulate metal.
The following example illustrates the invention:
De-oiled vacuum distilled naphthenic acids having an acid no. of about 178 mg. of KOH per gram and an SSU viscosity at 210 F. of about 106, were divided into three portions. The first portion was admixed with 1% by Weight of powdered aluminum, and the second portion with 1% by Weight of powdered magnesium. The third portion was not treated with these metals. All three samples were aged at 250 F. for 24 hours in contact with From these tabulated results it may be seen that both aluminum and magnesium are effective in improving naphthenic acid color stability. The improvement through theuse of aluminum was somewhat greater than that occasioned through the use of magnesium.
I claim:
1. The method for improving the color stability of naphthenic acids which consists of contacting-naphthenic acids with treating agent consisting essentially of particulate metal selected from the group consisting of aluminum and magnesium at a temperature in the range of 60 F. to 500 F.
2. The method for improving the color stability of naphthenic acids which comprises: storing naphthenic acids in admixture with treating agent consisting essential- -ly of particulate metal selected fromthe group-consisting of aluminum and magnesium at a temperature in th range of F. to 200 F.
3. The method for improving the color stability of naphthenic acids which consists of passing naphthenic acids through a bed of treating agent consisting essentially of particulate metal selected from the group consisting of aluminum and magnesium at a temperature in the range of 200 F. to 500 F.
4. The method according to claim 1 wherein said metal is aluminum.
5. The method according to claim 1 wherein said metal is magnesium.
6. The method for improving the color stability of naphthenic acids which comprises: storing naphthenic acids at a temperature in the range of 60 F. to 200 F. in admixture with treating agent consisting essentially of particulate metal selected from the group consisting of aluminum and magnesium, said metal having a particle size of -400 mesh (Tyler standard screen).
7. The method for improving the color stability of naphthenic acids which consist of passing naphthenic acids at a temperaturein the range of 200 F. to 500 F. through a bed of treating agent consisting essentially of particulate metal selected from the group consisting of aluminum and magnesium said metal having a particle size of 16-60 mesh (Tyler standard screen).
References Cited in the file of this patent V UNITED STATES PATENTS 2,528,803 Unkefer Nov. 7, 1950 2,573,049 Olson Oct. 30, 1951 2,582,833 Hunn Ian. 15, 1952

Claims (1)

1. THE METHOD FOR IMPROVING THE COLOR STABILITY OF NAPHTHENIC ACIDS WHICH CONSISTS OF CONTACTING NAPHTHENIC ACIDS WITH TREATING AGENT CONSISTING ESSENTIALLY OF PARTICULATE METAL SELECTED FROM THE GROUP CONSISTING OF ALUMINUM AND MAGNESIUM AT A TEMPERATURE IN THE RANGE OF 60*F. TO 500*F.
US447674A 1954-08-03 1954-08-03 Treatment of naphthenic acids Expired - Lifetime US2789999A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3150181A (en) * 1962-01-04 1964-09-22 California Research Corp Purification of aromatic acids using zinc, aluminum, or magnesium

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2528803A (en) * 1947-08-01 1950-11-07 Harshaw Chem Corp Preparation of metallic soaps
US2573049A (en) * 1950-08-31 1951-10-30 Harshaw Chem Corp Preparation of metal-organic compounds
US2582833A (en) * 1950-07-12 1952-01-15 Sherwin Williams Co Method for the preparation of aluminum and magnesium soaps

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2528803A (en) * 1947-08-01 1950-11-07 Harshaw Chem Corp Preparation of metallic soaps
US2582833A (en) * 1950-07-12 1952-01-15 Sherwin Williams Co Method for the preparation of aluminum and magnesium soaps
US2573049A (en) * 1950-08-31 1951-10-30 Harshaw Chem Corp Preparation of metal-organic compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3150181A (en) * 1962-01-04 1964-09-22 California Research Corp Purification of aromatic acids using zinc, aluminum, or magnesium

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