US2042718A

US2042718A - Method of refining hydrocarbon oils

Info

Publication number: US2042718A
Application number: US464350A
Authority: US
Inventors: Lachman Arthur
Original assignee: VAPOR TREATING PROCESSES Inc
Current assignee: VAPOR TREATING PROCESSES Inc
Priority date: 1930-06-27
Filing date: 1930-06-27
Publication date: 1936-06-02
Anticipated expiration: 1953-06-02

Description

june 2, 1936. A. LACHMAN METHOD OF REFININQ HYDROCARBON OILS Original Filed June 27, 1930 Q in Tim!

lNVENTOR HE THUE L/VC HNi/V BY Patented June 2, I936 UH I STATES ATENT OFFICE 2,042,718 METHOD OF REFINING HYDROCARBON OILS Arthur Lachman, Berkeley, Calif.,

mesne assignments, t esses Inc., a corporati assignor, by

0 Vapor Treating Procon of California Application June 27, 1930, Serial No. 464,350

Renewed Fe cracking or tion is a continuation in part of my pending apgasoline stock is With a Water solutlon of an alkali with water. This treatment removes most of the bruary 6,

corrosive sulphur compounds into non-corrosive bodies.

gasoline after the purifipounds into compounds that may be extracted to a high extent with the metal salt solution employed. Also which may assist in the polymerization of the unstable, unsaturated hydrocarbons and thereby produce a gasoline stock which is low in sulphur content, sweet to the doctor test and contains substantially no gums or gum forming constituents.

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 purification completed by methods known 1 art, such as treatment with caustic alkali, sulphuric acid, In case of gasoline stocks produced by cracking high sulphur bearing crude petroleum oil or residuum, it may be advantageous to treat such gasoline stocks with small amounts of sultreatment with a water any of the aiorestated metal salts or mixtures thereof, which may also be followed by treatment with an alkali water solution of sodium, potassium, or calcium hydroxide, carbonates of sodium or potassium.

Although a solution of less concentration 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 mixtures of salts employed is preferably a substantially concentrated solution and the temperature employed for the treatment is approximately 300 to 400 degrees F., which normally fluctuates, depending upon the vaporizing temperature of the oil under treatment.

One of the principal objects of this invention is to accomplish a desulphurization and purification of gasoline stock by a vapor phase treatment with a water solution of a metallic salt or salts at the reacting temperature in the presence of air.

Another object of the invention is to provide a. rapid and economical process for purifying gasoline stock produced by the thermo molecular decomposition of higher boiling petroleum oils by treating the same with an agent capable of polymerizing all of the unstable hydrocarbons contained therein and at the same time remove all the corrosive sulphur compounds and render the gasoline sweet to the doctor test.

Another object of the invention is to provide an economical method for improving the color, removing sulphur compounds, gums and gum forming material from gasoline or naphtha stocks, so that the same may be kept in storage for relatively long periods of time without change in quality by the formation of polymerized bodies.

Other objects and advantages will be apparent from the preferred embodiment of this invention which will now be more fully explained by reference to the accompanying drawing, which is a diagrammatical representation of an apparatus in which the invention may be carried out.

Referring to the drawing, it indicates a pipe leading to a source of crude gasoline vapors coming from a vaporizing chamber or fractionating tower not shown. Pipe iii is connected to jet mixer 14, the flow of crude gasoline vapors being controlled by operating valve ll. Pipe 15 controlled by valve !8 leads to an air supply not shown. The quantity of air introduced into the jet mixer l4 ranges from approximately 4 cubic feet to as much as 12 cubic feet or more, per barrel of liquid gasoline supplied calculated at 60 degrees F. and 760 mm. pressure, the quantity of air employed depending upon the extent of oxidation required to obtain a sweet gasoline substantially free from sulphur, gums and gum forming constituents. The air supply may also be measured as a percentage of the volume of vapors 5 being treated. The volume of added air normally varies from 0.5 to 1.5 per cent, measured at the same temperature and pressure as the vapors. Pipe 2 connects the jet mixer M to treating towe B at the point 9 below the contact 10 material 3. Pipe 8 controlled by valve 2| leads to a supply of water or steam not shown. Pipe !3 controlled by the valve 2% is connected to pipe 8 and leads to a source of air supply not shown, by means of which air may be introduced into treating tower B along with water or steam instead of through the pipe i5. 13 indicates in general a tower of suitable height and diameter filled with resistant or contact material such as fire brick, spiral tile, rock or the like, indicated by the numeral 3, which forms 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 I2 containing a water solution of a metallic salt or mixtures of the same, as heretofore enumerated, having a concentration of from 59 per cent or less to as high as approximately 85%. Preferably a substantially concentrated water solution of zinc chloride containing an oxide or hydroxide is employed, although a solution of less concentration may be used, the concentration depending upon the stock under treatment and the product desired. Tank i2 is connected to tower B by .means of a pipe 4, having a regulating valve 5. The pipe d 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 open, over the brick work or contact material. The water solution of the metallic salt or salts flows downward through this contact material and may finally be discharged through the bottom by a pipe 1, controlled by valve l9, to a storage not shown and may be thereafter recovered for reuse. As heretofore stated, tower B is provided with a steam or water inlet pipe 8, which may intermittently or continuously supply a predetermined amount of water or steam to the tower B. The hot gasoline vapors coming through the pipe it enters the mixer M wherein they are continuously mixed with the required amount of air coming through the pipe l5 regulated by valve I8. The quantity of air introduced may range from approximately 4 to 12 cubic feet or more per barrel of gasoline stock to be treated. From the mixer Hi the gasoline vapors commingled with the required amount of air passes through pipe 2 and enters the lower section of the tower B at a point 9. The gasoline vapors commingled with the introduced air pass up through the numerous tortuous passages in the brick-work and thereby come into intimate contact with the said water solution of metallic salt or salts flowing over the contact material 3. Although other temperatures may be employed, the water solution of metallic salt or salts, gasoline vapors and air are generally maintained at a temperature of approximately 300 to 400 degrees F. The purified gasoline vapors and air after passing through the tower B are discharged at the upper end of the tower B through a pipe it! which is connected with a condenser H of suitable construction. From condenser H the condensed purified gaso- 2,042,718 3 lin and i m products pas hr u h pip of water when a larger amount of a solution of certain amount of water from the water soluthe aeriform products, are sweet to the doction of the metallic salt or salts and the purpose tor test and suitable for use as refined gasoof the steam or water inlet 8 is that of mainline stock of high purity with a low sulphur containing the solution at approximately a certain tent.

water content so as to maintain the necessary While the process herein described is well said solution is admitted for each barrel of gaso- 11m oil from the aeriform productsline stock under treatment and a corresponding A process of refining mineral 011$, Comprisamount of the spent solution is withdrawn at vaporizing mineral 011 by the application the same time. The amount of water vapor reof heat, Commingling the ap zed mineral oil quired to replace the vaporized Water from the W th a and Contacting the heated vaporized water solution of metallic salt or salts varies mineral O nd the a W a ma ntained subwithin wide limits, depending upon th on stantially concentrated Water solution of zinc tration of the solution employed, the temperasalt other than zinc iod1de, separating, condensture at which the operation is carried out, the ing and collecting a purified mineral oil from nature and amount of the inert gases which products of reaction, treating solution and aeritreated and the air employed for the oxidizing 47 A process of refining mineral oils, comprisreaction. Approximately 50 to 100 pounds of ing, commingling vaporized mineral oil with air,

rified mineral oil from products of reaction, treating solution and aeriform products.

5. A process of refining mineral oils, comprising, vaporizing a mineral oil by the application of heat, contacting the heated vaporized mineral oil with a maintained heated water solution of a zinc salt other than zinc iodide and air and then separating, condensing and collecting a purified mineral oil from products of reaction, treating solution and aeriform products.

6. A Process of refining mineral oils, comprising, vaporizing a mineral oil by the application of heat, commingling the vaporized oil with a maintained water solution of a zinc salt other than zinc iodide in the presence of air, heated to a temperature of not less than the vaporizing temperature of the vaporized mineral oil under treatment, and then separating, condensing, and collecting a purified mineral oil from products oi reaction, treating solution and aeriform products.

'7. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor at a temperature of approximately 300 to 400 degrees F., contacting the heated vapor with a maintained'water solution of zinc salts other than zinc iodide and air maintained at a substantially similar temperature, then condensing and collecting a purified mineral oil, separated from products of reaction, treating solution and aeriform products.

8. A process of refining mineral oils, comprising, commingling a mineral oil vapor at temperatures of approximately 300 to 400 degrees F., with air and a maintained water solution of zinc salt other than zinc iodide maintained at a substantially similar temperature, the water solution of zinc salt having a concentration of approximately 50-85 then condensing and collecting a purified mineral oil, separated from products of reaction, treating solution, and aeriform fluids.

9. A process of refining mineral oils, comprising, heating, a mineral oil to form a vapor, contacting the heated vapor commingled with air, with a maintained water solution of zinc salt other than zinc iodide containing zinc hydroxide and then separating, condensing and collecting a purified mineral oil from products of reaction, treating solution and aeriform fluids.

10. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor commingled with air through and in contact with a maintained water solution of zinc salts other than zinc iodide containing iromJ/ of 1 per cent to 3 per cent by weight of zinc hydroxide and then separating, condensing and collecting a purified mineral oil, from products of reaction, treating solution and aeriform fiuids.

11. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor commingled with air through and in contact with a maintained water solution of zinc salt other than zinc iodide containing from of 1 per cent to 3 per cent by Weight zinc hydroxide and zinc oxide and then separating, condensing and collecting a purified mineral oil from products of reaction, treating solution and aeriform fiuids.

12. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor commingled with heated air through and in contact with a water solution of zinc salts other than zinc iodide, maintaining the solution in a fiuid condition by the additions of water, condensing and collecting a purified vapor of the mineral oil after passing through the solution.

13. A process of refining mineral oils, comprising, commingling the vapors of a mineral oil containing air with a maintained water solution of 5 zinc salt other than zinc iodide and then condensing and separating treated mineral oil vapors from aeriform products.

14. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing 10 the heated vapor containing air through and in contact with a water solution of zinc salt other than zinc iodide containing zinc hydroxide, maintaining the solution in a fluid condition by the addition of water during contact of the vapors and 15 air with the treating solution and condensing the vapor after passing through the solution.

15. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor commingled with air through 20 and in contact with a water solution of zinc salts other than zinc iodide containing from of 1 per cent to 3 per cent by weight of zinc hydroxide and zinc oxide, maintaining the solution in a fluid condition by addition of Water during contact of 25 the vapors and air with the treating solution and condensing the vapor after passing through the solution.

16. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, pass- 30 ing the heated vapor commingled with air through and in contact with a. water solution of zinc salts other than zinc iodide, maintaining the concentration of the solution within predetermined limits by the addition of water, condensing and col- 35 lecting the refined mineral oil vapors after passing through the solution.

17. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor at a temperature of approximately 300 to 400 degrees F., passing the heated vapor commingled with air through and in contact with a water solution of zinc salts other than zinc iodide maintained at a similar temperature and having a concentration of approximately 59-85%, 45 maintaining the concentration of the solution as specified, by the continuous addition of water and then condensing the refined mineral oil vapors after passing through the solution.

18. A process of refining mineral oils, comprising, vaporizing a mineral oil, contacting the vaporized mineral oil commingled with air with a water solution of zinc salt other than zinc iodide, intermittently introducing water into the solution of zinc salt to maintain the salt in solution and continuously condensing and collecting purified mineral oil vapors separated from the products of reaction, aeriiorm fiuids and solution of zinc salt.

19. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the vapor commingled with air through and in contact with a water solution of zinc salts other than zinc iodide containing zinc hydroxide, intermittently introducing Water into the solution of zinc salts containing zinc hydroxide to maintain the salts in solution and continuously condensing and collecting purified mineral oil vapors separated from the products of reac- 70 tion, solution of zinc salts and 'aeriform fiuids.

20. A process of refining mineral oils, comprising heating a mineral oil to form a vapor, passing the vapor commingled with air through and in contact with a water solution of zinc salt 75 other than zinc iodide containing zinc oxide, inand then condensing and separating the mintermittently introducing Water into the solution era] oil from aeriform products. OI zinc salt containing zinc oxide to maintain 2. A process of refining mineral oils comthe treating solution, products of the reaction tacting the commingled vapors and air with a and aeriform products. maintained water solution of heavy metal salt