US2331343A - Refining of mineral oils - Google Patents

Description

C512, 1943- G. E. PHILLIPS I REFINING OF MIiIERAL OILS Filed Dec. 17, 1940 Patented Oct. 12,1943

UNITED STATES PATENT OFFICE 2,331,343 g REFINING OF MINERAD oILs- Y Gerald E. Phillips, Cranford, N. J., assignor to Standard Oil Development Company, a corporation of Delaware Application December 17, 1940, Serial No. 370,461 9 Claims. (01. 196-28) The present invention relates to a process for ferred temperature. When operating in this refining mineral oils. The invention is more parmanner, a portion of the exothermic heat is ticularly concerned with the production of imtaken up by the feed stock and undesirable proved motor fuels having high anti-knocking degradation of the feed stock is prevented. It

scission of the same. However, due to the fact that the reaction when desulfurizing oils of this character is exothermic, it has been extremely difficult to maintain the temperature in the-reaction zone within the critical temperature range desired. 'In order to control the temperature within the desired operating range, various proposals have been made. It has been proposed that the feed stock be introduced into the bauxite-treating zone somewhat below the precharacteristics as measured by a high ,octane 5 has also been proposed to utilize various cooling number, by an operation which comprises? bauxmeans, such as cooling coils and the like, ite-treating petroleum feed oils under carefully throughout the reaction zone. This, however, controlled conditions.=s. In accordance with the has not been entirely satisfactory due to the fact present invention, petroleum oils are processed that in order adequately and positively to control under conditions adapted to produce products the temperature of the reaction, the feed zone boiling in the motor fuel boiling range, which are must have a relatively small diameter. I have, characterized by having relatively highoctane however, now discovered a process by which it is numbers and relatively low sulfur concentrations. possible to positively control the temperature of These products are produced by passing a suitthe reaction throughout the reaction zone within able feed oil through a bauxite bed within a the desired narrow critical temperature range. critical temperature range which is controlled by In accordance with my process, the temperature introducing, preferably at a plurality of stages, within the treating zone is maintained substana liquid, preferably water, in relatively small tially constant by taking out the exothermic heat amounts. of reaction by the use of a cooling liquid which It is known in the art to subject various petrois preferably introduced at a plurality of stages. leum oil feed stocks, such as heavy naphthas, gas The process O y invention y be readily oils, reduced crudes, and the like, to temperature n o d y reference t the attached r win and pressure conditions adapted to produce relaillustrating modifications of the same. For purtively lower boiling constituents and relatively poses of illustration, it is assumed that the feed higher boiling constituents. It is also known in oil comprises a cracked petroleum distillate boilhe art to refine the resulting products by treating ins in the motor fuel boiling r nge. The feed oil the same with various acids, clays, metallic s ntr d d t atin il or qu nt oxides, such as bauxite, and the like. For exm a s I by m s f f d line n h at n ample, it is known to remove objectionable sulfur ,coil l the feedoil is raised to the desired temcompounds from petroleum oils, particularly from Pe p f ly in the ran e 01 about 700 F- petroleum oils boiling in the motor fuel boiling t0 The feed 011 is Withdrawn by means range, by contacting the same with bauxite at of line 3, introduced into bauxite treating zone elevated temperatures which vary over a-rela and passed downwardly through reaction n tively wide temperature range. In these operaand Withdrawn by means of line 9. The retions it has been found that, providing the temaction being exo h r the mpe e nd perature of the bauxite-treating operation be to r se- In a c d w y P 81119211 controlled within a relatively narrow critical quantities Of a liquid are introduced at a D temperature range, not only will the petroleum a ty of points t eacti e 5 by e s oils be desulfurized in an efllcient and economof lines 7 and p c ve y T e treated ical manner, but the treated feed stock will have 40 oil withdrawn from reaction zone 5 by means of unexpected, desirable properties which could not a lin 9 y e u th dl d r r fin d in y b .foreseen from di l ur s in th prior rt, manner desirable. It is to be understood that These improvements apparently are secured by auxite c n a tin zone 5 may mpris any suita chemical rearrangement of the molecules, such able be and a a e of Contacting as isomerization, dehydrogenation, and perhaps units- The process of the present invention may be widely varied. The invention essentially com prises desulfurizing a petroleum oil by passing --.the same through a bauxite-treating zone and volume of bauxite per hour.

may be any desired particle size. I have found it is desired to control the temperature within a narrow critical temperature range. The invention is particularly applicable in bauxite. desulfurization of cracked petroleum feed oils boiling in the motor fuel boiling range.

In these operations, it is desirable that the temperature in the reaction zone be controlled in the range from about 600 F. to 900 F., preferably in the range from about 750 F.' to 820 F. The operation, in general, is conducted under substantially non-cracking conditions. Thus, when treating high refractory stocks, the desulfurization operation may be conducted at temperatures as high as 900 F. without securing any substantial cracking of the feed oil.

The cooling fluid added at a plurality of stages may be varied widely. The cooling fluid, however, preferably comprises water in the liquid or vaporous state. A particularly desirable cooling fluid comprises wet steam. In general, we have found that it is preferred to introduce the water at at least three stages, and to introduce approximately 0.1% of water by weight, or 0.5% of steam by weight, based upon the feed oil. Particularly desirable results are secured by utilizing a plurality of thermostats or equivalent means in the path of flowing vapors immediately preceding the respective points of introduction of the cooling fluid, in a manner adapted to regulate and control the flow of the cooling fluid introduced at the particular point.

The bauxite preferably comprises a native aluminum hydroxide containing from 50% to 70% of A120: and from to of water. In general, it is preferred that the bauxite be activated by burning the same at a temperature in the range from about 500 F. to 1100 F., preferably at a temperature in the range from about 600 F. to 900 F. The feed rates may va y considerably depending upon the general operating conditions, the character of the feed oil being treated, as well as upon the type of bauxite employed. In general, the feed rates are in the range from about 1 volume to 10 volumes of oil per volume of bauxite per hour. The preferred rates are from about 2 to 4 volumes of oil per The bauxite also that granular bauxite is desirable.

In order to illustrate the invention further, the following example is'given which should not be construed as limiting the same in any manner whatsoever:

Example Various operations were conducted in which cracked feed oils, having a gravity of 60 A. P. I. and which boiled in the motor fuel boiling range,

Amount of water or steam injected at a plurality of stages into the reactor to give an average catalyst temperature of 800 F.

What I claim as new and wish to protect by Letters Patent is as follows:

1. Process for removing objectionable sulfur compounds from petroleum oils, which comprises passing the petroleum oil in the vaporous state through a bed of bauxite, and removing the heat of reaction by the introduction of a cooling fluid comprising water at a plurality of stages, the

total amount of water introduced being not j greater than about 0.5% based upon the quantity of oil being treated per unit of time.

2. Process as defined by claim 1, in which said petroleum oil is a cracked petroleum naphtha boiling in the motor fuel boiling range, and in which said petroleum oil is contacted with the bauxite at a temperature in the range from about 600 F. to 900 F.

3. Process for removing objectionable sulfur compounds from petroleum oils, which comprises passing the petroleum oil in the vaporous state through a bed of bauxite, and removing the heat of reaction by the introduction of wet steam at a plurality of points, the total amount of water introduced being not greater than about 0.5% based upon the quantity of oil being treated per unit of time.

4. Process as defined by claim 3, in which petroleum oil comprises a cracked naphtha boiling in the motor fuel boiling range.

5. Method of controlling the temperature of a treating process, in which a mineral oil is treated by passing the same through a bed of bauxite catalyst and exothermic heat is thereby evolved, which comprises introducing water as a cooling fluid into the catalyst at a plurality of points, the

total amount of water introduced being not greater than about 0.5% based upon the quantity of oil being treated per unit of time.

6. Method as defined by claim 5, in which the treating process comprises a desulfurization reaction. I

'7. Method as defined by claim 5, in which about 0.1% of liquid water is introduced into the catalyst.

8. Method as defined by claim 5, in which about 0.5% of steam is introduced into the catalyst.

9. The process as defined by claim 1. in which the water is introduced in at least three stages and in which the amount of water introduced into each stage is thermostatically controlled so that the temperature within the catalyst bed is maintained at about 600 to about 900 F.

GERALD E. PHILLIPS.

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