US1809170A

US1809170A - Process of refining hydrocarbon oils

Info

Publication number: US1809170A
Application number: US361513A
Authority: US
Inventors: Lachman Arthur
Original assignee: RICHFIELD OIL Co
Current assignee: RICHFIELD OIL Co
Priority date: 1929-05-08
Filing date: 1929-05-08
Publication date: 1931-06-09
Anticipated expiration: 1948-06-09
Also published as: US1826147A; US1826139A; US1826144A; US1826140A; US1826146A; US1826145A; US1826141A; US1826143A; US1826142A

Description

June 9 1931' LACHMAN. 1,809,170.v I Pnocnzssl oF REFINING HYDRocAnBoN OILS Filed May 8. 1929 Patented June 9, v1931 UNITED STATES 'PATENT OFFICE' ARTHUR LACHMAN, Fl BERKELEY, CALIFORNIA, .ASSIGrN'OR T0 RICEFIELD OIL COM- WARE Application led May 8,

This invention relates to a process of purifying and refining hyd-rocarbon oils obtained by distillation or cracking vof mineral oils, such as lubricating oils, lamp oils, gasoline stocks or distillates derived from oil shale. This application is a continuation in part of -my pending application SerialA No. 200,589, filed June 22, 1927 for method of relining mineral oils, which consists of a similar method or process for purifying and rening mineral oil products with a Water solution of zinc chloride.

The process of refining hydrocarbon oils, as described in this application, is applicable to all mineral oil products derived by distillation or cracking operations, such as lubricating oils, lamp oil stocks, gasoline stocks distillates derived from oil shale, etc., an is particularly adaptable to gasoline stocks 2 obtained by cracking higher boiling hydrocarbon oils. For the purpose of simplifying the description, reference will be made 'to gasoline only.

Crude gasoline stocks obtained by distilling. or cracking petroleum oils consist of a mixture of saturated and unsaturated hydrocarbons together with sulphur compounds, nitrogen bases and other substancesl of an ,nundeined nature.

s are readily oxidizable at ordinary temperatures and are usually responsible for the change of color which takes place when rened gasoline is stored. These oxidizable substances are removed With diiiculty when 5 gasoline stocks are treated by the methods known in common use.

ln order to show the nature of my invention, it is desirable to describe the method now in common use in oil reneries, and.

(m particularly that step of refining gasoline stocks which consists in deodorizing and stabilizing the same. Crude gasoline stocks obtained by distillation of crude petroleum oil or by cracking a higher boiling petroleum oil, are customarily treated With approximately from l per cent to as high as 8 per cent by Weight sulphuric acid, the quantity of sulphuric acid depending upon the nature of the gasoline stock to be treated and the product desired. This acid treatment usual- These latter substances wiPANY or CALIFORNIA, or Los ANGELES, cAmronNrA, A CORPORATION on DELA- PRooEss or REFINING HYDRocARBoN OILS ya 'I 1929. Serial No. 361,513.

ly consists in commingling the gasoline Stock With the required amount of sulphuric acid .necessary to obtain the desired extraction, either by the Well-known batch Aor continuous treatment, after Which the products of the acid reaction are permitted to settleiand then Withdraw from the treated gasoline stock. The acid treated gasoline stock is then neutralized by Washing with a Water solution of an alkali and nally with Water. This treatment removes most of the impurities, but subsequent treatments areusually necessary to deodorize and remove or convert corrosive Sulphur compounds into noncorrosive bodies. For this purpose, a Water solution of sodium plumbite or sodium hypochlorite is usually employed to render the gasoline sweet to the doctor test.

The general objections to a treatment of this character are as follows:

(l) Gasoline purified by this method frequently becomes discolored when stored for a period of time;

(2) considerable quantities; of sulphuric acid are required, which are difficult to recover; K A

(3) as high as 10 per cent of the valuable stable unsaturated hydrocarbons contained in the gasoline stock may be lost; and

(4:) the treatment must frequently be followed by a deodorizing or sweetening process, such as that heretofore described.

Now, l have discovered that the sulphuric acid normally used to treat crude gasoline stocks may be reduced to a high extent, and in many cases may be entirely eliminated by the employment of a water solution of certain metallic salts, or mixtures of the same, which may be zinc, copper, cadmium, mercury, iron, chromium, manganese, aluminum, nickel or cobalt Water soluble salts, Such as the chloride, bromide, iodide, sulphate, nitrate, and also any of the Water soluble salts ofthe above named metals of organic acids, such as the sulphonic acids of benzol, toluol and xylol, or the sulphonic acids derived from the treatment of petroleum oils with sulphuric acid.

The process described briefly consists in passing the hydrocarbon oil product such as gasoline lstock while in a vapor state, through or in contact with a hot concentrated water solution of any of the aforesaid yao metallic salts or mixtures thereof. The gasoline stock so treated is usually pure enough for immediate use, although it sometimes may contain small'amounts of hydrogen sulphide, which may be removed by washing with an alkaline solution of sodium or calcium hydroxide, or the carbonates of sodium or potassium.

The hydrocarbon oil stock to be treated by my invention may or may not have had a preliminary treatment with sulphuric acid, or other agents to partly purify the same, or may be first partly purified by my invention and the purifications completed by methods known in the art, such as treatment with caustic alkali, sulphuric acid, etc. lin case ofgasoline stocks produced by cracking high sulphur bearing, crude petroleum oils or residuums, it may be advantageous toI treat such gasoline Stocks with small amounts of sulphuric acid before the treatment with a concentrated water solution of any of the afore-stated metallic salts, which may also be followed by treatment with an alkaline water solution of sodium, potassium or calcium hydroxide, or the carbonates of sodium or potassium.

Although a solution of less concentratio may be employed which may range from 50 or less to approximately 85 per cent, the

strength of the water solution of the metallic salt or mixture of salts employed is preferably a substantially concentrated solution, and the temperature employed for the treatment is approximately 300 to 400 degrees iF.,

which normally fluctuates, depending upon the vaporizing temperature of the oil under treatment.

With the foregoing preliminary ex lanation, the preferred embodiment of my invention will now be more fully explained by reference to the accompanying drawing which is a diagrammatic view of one form ofapparatus which may be employed for carrying out the objects of the present invention.

Referring to the drawing, 2 indicates a pipe leading to a source of crude gasoline vapors not shown, such as a fractionating tower employed to separate the lower boiling oils from the'higher boiling4 oils. B indicates a tower of suitable height and diameter filled with resistant orcontact material, such as fire brick, spiral tile or the like, indicated at 3, which forms numerous tortuous passages through the tower, although it is to be. understood that the well-known bubble cap contact tower may be employed. Disposed above the tower or adjacent to the same, is a tank l2 containing a substantially concentrated water solution of a metallic salt or mixtures of the same, as heretofore enumerated, having a concentration of from asoaivo 50 per cent or less to as high as approximately 85 per cent. This tank is connected to the top of the lower by means of a pipe 4 having a regulating valve 5. This pipe terminates over a spreader plate 6 and this plate evenly distributes the water solution of the metallic salt or salts when the valve 5 is opened, over the brick work or contact material.' The water solution of the metallic salt or salts flows downward through this contact material andv may finally be discharged through the bottom by a pipe 7, after which it is treated for recovery. 'lhe tower B is also provided with a steam or water inlet pipe 8, which intermittently or continuously supplies a predetermined amount of water or steam to the tower. The hot gasoline vapors from the' pipe 2 enter the lower end of the tower B at a point 9. rlihey oil vapors pass up through the numerous contact passages in the brick work and thereby come into intimate contact with the said water solution of metallic salt Aor salts flowing over the same. temperatures may be employed, both the Water solution of metallic salt or salts and oil vapors are generally maintained at a temperature of approximately 300 to 400 degrees F., and the oil vapors are discharged at the upper end of the tower through a pipe 10 which is connected with a condenser- 11 of suitable construction. The gasoline vapors passing through the contact tower B at the temperature s ecified, vaporize a certain amount of water rom the water solution of metallic salts and the purpose of the steam or water inlet pipe 8 is that of continuously maintaining the solution ata certain water content so as to maintain the necessary Huidity which is essential for good contact between the. rising gasoline vapor and the down-flowing water solution of metallic salt or salts. the water solution of metallic salt or salts is maintained at its predetermined -limits of concentration by a continuous introduction of water or water vapor. Otherwise solid metallic salt or salts and solid sludge impurities may plug the passages through which the gasoline vapors are being conducted.

While not always necessary, it is beneficial that the water solution of metallic salt or salts contain hydroxides or oxides of' any of the metals, or mixtures thereof, heretofore enumerated, before being introduced into the system. This may be accomplished by agitating the Water solution of the metallic salt or salts with any of the hydroxides or oxides of any of the enumerated metals. The optimum amount of the metal oxide or hydroxide ranges from about 1/2 of l per cent to 3 per cent by weight of the water solution of metallic salt or salts. tion, when the oxides or hydroxides of any Although other Preferably the concentration of of the aforementioned .metals or mixtures thereof are soluble in substantial amounts in the salt or salts solution at' the temperatures and pressures employed, it is no doubt that the beneficial action will be enhanced but even if no vsubstantial solubility exists, useful effects can be obtained if the oxides and hydroxides are suspended in the salt or salts solution.

The reaction tower B is kept full of the Water solution of the metallic salt or salts containing metallic hydroxides or oxides suchV as zinc hydroxide, and. a fresh' supply of approximately 15 pounds of the said solution is admitted for each barrel .of gasoline stock under treatment and a corresponding amount of the spent solution is Withdrawn at the same time.

v The amount of Water vapor required to replace the vaporized water from the Water solution of metallic salt or salts varies Within Wide limits, depending upon the concentration of the solution employed, the temperature at which the operation is carried out and the nature and amount of'inert gases which may accompany the gasolinev vapor being treated. Approximately 50 to 100 pounds of Water or Water vapor will usually be suficient` for each barrel of gasoline stock treated. By this treatment the major portion of the impurities contained by the gasoline stock Ais removed and carried out With the Water solution of metallic salt or saltsv as a sludge and the purified gasoline vapors,

when condensed, are suitable for use as a refined gasoline stock of high purity.

While the process herein described is well.

ladapted for carrying out the objects of the claims.

What I claim is:

1. A process of refining mineral oils, comprising, vaporizing a mineral oil, contacting the vaporized oil with a water solution of a zinc salt maintained in solution and then condensing purified oil vapor separated from products of reaction and treating agent.

2. A process of refinlng mineral oils, c'olnprising, vaporizing a mineral oil by theiapplication of heat, contacting the heated vaporized mineral oil with a substantially concentrated solution of a zinc salt maintained in solution and then condensing purified oil vapor separated from products of reaction and treatin agent.

3. A process of re ning mineral oils, comprising, vaporizing a mineral oil, contacting the vaporized mineral oil with a Water solution of a mixture of zinc salts maintained-in solution and then condensing purified oil vapor separated from products of reaction and ltreatin agent.

4. A process of re Yning mineral oils, comprising, vaporizing a mineral oil by the application of heat, contacting the heated vaporized mineral oil With a heated Water solution of a zinc salt maintained in solution and then condensing purified oil vapor separated from products of reaction and treating agent.

5. A lprocess of refining mineral oils, comprising, vaporizing a mineral oil by the application of heat, contacting the heated vaporized mineral oil with a heated Water solution of a zinc salt maintained in solution and heated to a temperature of not less than the vaporizing temperature of the vaporized mineral oil under treatment, and then condensing purified oil vapor separated from products of reaction and treating agent.

6. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor at vtemperatures of approximately 300 to 400 `degrees F., contacting the heated vapors with a Water solution of a zinc salt maintained in solution at a substantially similar temperature and then condensing purified oil vapor separated from products of reaction and treating agent.

7. A process of refining mineral oils, comprising, heating a lmineral oil to form a vapor at temperatures of approximately 300 to 400 degrees F., passing the heated vapors through or in contact with a Water solution of zinc salts maintained in solution at a substantially similar temperature and having a concentration of approximately 50-85% and.v

then condensing purified oil vapor separated from products of reaction and treating agent.

8. A process of refining mineral oils, co1n. prising, heating a mineral o1l toform avapor, contacting the heated vapor with a water solution of zinc salts maintained in a fluid condition and containin zinc hydroxide, and then condensing purified oil vapor separated from products of reaction and treating agent.

9. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor through and in contact with a Water solution of zinc salts, maintaining the solution in a fluid condition bythe addition of Water and condensing the vapor after passing through the solution.

10. A process of refining mineral oils, comprising, commingling the vapors of a mineral .oil With a water solution of a zinc salt maintained in a fluid condition and then condensing purified oil vapor separated from products ofreaction and treating agent.

11. A process of refining mineral oils, comprising, heating a-mineral oil to form. a vapor, passing the heated vapors through and in contact With a Water solution of a zinc salt containing zinc hydroxide, maintaining the solution in a fluid condition by the addition of Water during contact of the vapors With the treating solution and condensing'the vapor after passing through the solution.

12. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor through and in contact with a Water solution of zinc salts containing from 1/2 of 1 per cent to 3 peil cent by Weight of Zinc hydroxide and zinc oxide, maintaining the solution in a Huid condition by addition of Water during contact of the vapors With the treating solution and condensing the Vapor after passing through the solution.

13. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor through and in contact With a Water solution of zinc salts, maintaining the concentration of the solution within predetermined limits by the addition of Water and condensing the vapors after passing through the solution.

14.' A process of refining mineral oils, comprising, heating a mineral oil to form a vapor at temperatures of approximately 300 Ato 400 degrees F., passing the heated vapor tion of a zinc salt, intermittently introduc-lv ing water into the solution of zinc salt to maintain the aqueous solution and continu'- ously condensing vapors of the purified mincral oil separated from the products of reaction and solution of zinc salt.

16. A process of refining mineral oils,

v comprising, heating a mineral oil to form a vapor, passing the vapor through and in contact with a water solution of zinc salts containing zinc hydroxide, intermittently introducing Water into the solution of zinc salts to maintainthe aqueous solution containing zinc hydroxide and continuously condensing the vapors of the vpurified mineral oil separated from the products of reaction and solition ofzinc salts' containing zinc hydrox- 1 e.

17. A process of refining mineral oils,

comprising, heating a mineral oil to form a 4 1n testimony whereof ll ax my signature.

ARTHUR LACHMAN.

through and in contact with a water solution