US1760585A - Process of refining hydrocarbons - Google Patents

Description

May 27, 1930. R. cRoss PROCESS OF REFINING HYDROCARBONS Filed Nov. 21, v1923 INVENTOR,

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/ AUM/1w zdf/9265's Patented May 27, 1930 ROY CROSS, 0F KANSAS CITY, MISSOURI,

ASSIGN'OR TO GROSS DEVELOPMENT COB,-

PORATION, A CORPORATION OF DELAWARE PROCESS OF REFINING HYDROCAEBONS Application filed November 21, 1923. Serial No. 676,027.

This invention relates to improvements in a process and apparatus for treating oils, and is particularly adapted to the treatment of distillates, either cracked or otherwise, recovered by distillation or cracking, but eii'ective in removing the sulphurcontent of the hydrocarbons besides deodorizing, decoloriz* ing and sweetening the oil to produce a marketable product.

Among the salient objects of the invent-ion are to provide a process inwhich oil is heated to relatively high temperature and maintained in a liquid phase, during the heating, by the imposition osel-imposed pressure of the generated gaseous vapors evolved during the heating thereof; to provide a process in which the oil, in this heated condition, is passed through a body, or bed, of treating material comprising a mixture of an adsorbing agent with a metallic salt, the latter having a particular ainity for sulphur compound; to provide an apparatus for carrying out this process, and, ingeneral, to provide' a process and apparatus of the character referred to.

In the drawing:

The single figure is a diagrammatic side elevational view of one type of apparatus which may be used in carrying out this invention.`

Referring brieily to the drawing, 1 is a heating coil positioned in a furnace 2, which is preferably heated by'means of gas burners diagrammatically shown at 3. 4 is an insulated retort, or chamber, in which the heated oil is collected and has connection with the treating towers 5 and' 6 through the line 7 and manifolding hereinafter explained. The outlet lines of the towers are likewise maniolded and connected through a line 8 to a cooling coil 9 positioned in the water cooling box 10. The discharge end of the coil, terminating in a pipe 11, is connected with a collecting tank 12. v

Referring now to the manner in which the oil is treated, a distillate, such as unrefined gasoline distillate or what is termed as benzine distillate commercially, is introduced through the inletpipe 13- and is charged by means of the pump 14 to the heating coil 1, where it is raised to a temperature at which the oil may be most e'ectively treated. lt is appreciated that dierent oils will require rather than in the vapor phase and for this reason a seliimposed pressure is maintained upon the oil which is collected on its discharge from the heating coil in the chamber 4.

Pressures of from 25 to 500 pounds are normally suiiicient to prevent substantial vaporization of the products to be treated. The

chamber is equipped with a pressure gauge 14 for registering the pressure therein.

From the chamber 4, the oil is discharged through the 'line 7 A by-pass line 15 controlled by a pop valve 16, communicates between the chamber 4 and the line 7 beyond the valve 17. In this transfer line is also interposed a thermometer 18 for ascertaining the temperature of the oil as it is discharged from the chamber. The transfer line 7 is connected to a header 19 which has secondary connections 20 and 21, regulated by valves 22 and 23 respectively, communicating with the separate towers 5 and 6.

The towers, as shown, consist preferably of cylindrical shells which are steam-jacketed in order that the desired temperatures may be maintained in the towers in order to produce the most eiicient and eective treatment. In operation, the oil discharge-d from the chamber 4 is directed to one of the towers, such as the tower 5, while the tower 6 is eliminated from the system by closing the valve 23. The oil, on being introduced to the tower 5, rises passing through a screen 24 positioned near the lower part of the tower and which supports the treating material. A similar screen 25 is positioned near the top pf the tower and prevents the oil from carrying off the treating material with it as 1t passes over to the cooling coil.

, The treating material in the tower shown diagrammatically as fragmentary or brolgen material, consists of a mixture of dried hydrous silicate of alumina with a metallic salt. It is desirable that the silicate of alumina be an active adsorbing agent, the

' best results having been procured by the use of a silicate of alumina occurring naturally and commercially known as bentonite. Good results also have been obtained with fullers earth, and other forms of silicate of alumina, but none of these latter mentioned materials seem to have the active adsorbentqualities of the bentonite. The metal salt used may be either a salt of copper, zinc, manganese, antimony, or other metals which have an affinity for sulphur. Copper salts have given particularly good results in combination with the bentonite. In making the mixture, it is desirable to have the metal salt intimately intermixed and uniformly dispersed in comminuted form through the adsorbent material. To effectively produce such a mixture,

it has been found advantageous to dissolve the metal salt first in a vehicle or a solvent material to form a solution and mix the solution with the silicate of alumina to form' a jell, after which the solvent is dried out. When combined in this manner, the metal salt is found to be uniformly dispersed if a thorough mixture of the solution with the adsorbing agent has been made. The minute particles of the metal salt, which have an active affinity for sulphur, are deposited from the solution, with the elimination of the solvent, onto the adsorbent material. The importance of this latter material, and a factor of importance in its adsorbent qualities, is the tremendous amount of surface it presents to the oil undergoing treatment. This increased surface correspondingly improves and increases the activity of the metal salt which is deposited upon the adsorbent material when the solvent is removed. These particles of metal salt, being in such a fine state of comminution, as a result have a greatly increased susceptibility and an increased activity which improves and augments the functioning of the metal salt with reference to its treatment of the hydrocarbons. Thus there is produced, from the treatment of the oils with this gel comprising a combination of a highly adsorbent material and a metal salt, a better quality and more completely refined material. This dried hydrous silicate of alumina is then placed in the tower between the screens as described, and the oil caused to rise through the treating material to the top of the tower where it is drawn ofrl through line 26 controlled by a valve 27. This line communicates with a line 8, connected with the cooling coil, and after cooling, the treated product is collected in the tank 12.

The function of the two towers is to facilitate the continuous operation of the process. By closing the valve 22, in the line 20, and the valve 27, in the line 26, the tower 5 may be cut out of the system and the treating mixture removed to be regenerated, as with continued use its activity will gradually diminish. The tower 6 is cut into the system by opening the valve 23 in the line 21 and the upper drawofl:l line 28, by opening the valve 29. Thus, while one tower is being cleaned and the material regenerated, the corresponding tower may be utilized. The towers are preferably jacketed in order that temperatures ascertained by the thermometers 30 may be controlled within themost efective range. The towers are also equipped with steam injected lines 31 controlled by valve 32.

To regenerate the mixture, it is preferably removed from the towers and roasted, or it may be treated with chlorine gas or with an oxidizing gas. The type of regenerating treatment will depend considerably upon the character of the metal and silicate of alumina used. In roasting or dehydrating the treating material, it is necessary to limit the temketable products and did not discolor on'A standing.

When treating benzine distillates where as subsequent distillation is necessary to recover a satisfactorv marketable gasoline-like product. the cooling coil may be omitted and the treated material introduced while hot direct from the treating tower to a still or distilling means not shown.

I claim as my invention:

l. A process for'treating hydrocarbon oil, consisting in heating the oil to a temperature above 200 F. and not in excess of 600 F. while maintaining thereon suicient pressure commensurate `with the temperature of the oil to maintain it in substantially the liquid pbase. passing the oil thence through a bed of refining material comprising a mixture of dried hydrous aluminum silicate intimately intermixed with a metal salt.

2. A process for treating hydrocarbon oil, consisting in heating the oil to a temperature about 200 F. and not in excess of 600 F. while maintaining thereon sufficient pressure commensurate with the temperature of the oil to maintain it in substantially the vliquid phase, passing the oil thence under reduced pressure through a bed of refining material of dried hydrous aluminum silicate in a colloidal form with a metal salt dispersed therethrough, and separating the treated oil and treating material.

3. A process for treating hydrocarbon oil, consisting in heating the oil to temperatures of from 200 F. to 600c F. While maintaining thereon suiilcient pressure commensurate with the temperature of the oil to maintain it in substantially the liquid phase, passing the oil thence through a mixture of bentonite and a lo metal salt and separating the oil and treating material.

4. A process for treating hydrocarbon oil, comprising the steps of heating the oil to 600 F. as a maximum and subjecting it to sucient 15 pressure to maintain it in the liquid phase at the temperatures used, filtering the oil through a mixture of a highly adsorbent dried hydrous aluminum silicate and intimately combined with a metal salt adapted toremove 2@ the sulphur ingredients therefrom, separately collecting the treated oil from the treating material. v

5. A process for treating hydrocarbon oil, comprising the steps of heating the oil to 600 2a F. as a maximum and subjecting it to suiiicient pressure to maintain it in the liquid phase at the temperatures used, ltering the oil through a mixture of bentonite intimately combined with a metal salt adapted to remove the sulphur ingredients therefrom, separately collecting the treated oil from the treating material.

6. A process for treating hydrocarbon oil, comprising the steps of heatingthe oil to 600 F. as a maximum and subjecting it to suicient pressure to maintain it in the liquid phase at the temperatures used, filtering the f oil through a mixture of a highly adsorbent 1dried hydrous aluminum silicate and intimately combined with a copper salt adapted to remove the sulphur ingredients therefrom, separately, collecting the treated oil from the treating material.

, 7. A process for treating hydrocarbon oil. comprising the steps of heating the oil to 600 F. as a maximum and subjecting it to sufcient pressure to maintain it in the liquid phase at the temperatures used, filtering the oil through a mixture of bentonite intimate-V i ly combined with a copper salt adapted to remove the sulphur ingredients therefrom, separately collecting the treated oil fromthe treatingmaterial.

ROY CROSS.

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