387. Analyses of some Illinois Crude Oils. H . M. Sm ith. U .S. B ur. Mines. R eport of Investigations N o. 3532, D ecem ber 1940.— B y virtue of im portant discoveries of new oil-fields m ade in 1937, Illinois is now one of the m ost prolific oil-producing areas in the U nited S ta te s. T h is report em bodies the results of analyses of thirty-five samples of petroleum from these new fields, and also includes an alyses of seven sam ples from fields developed before 1936. T h e sam ples an alysed represent three geographically different producing areas in the S ta te — nam ely, the eastern boundary in Clark, Crawford, Law rence, E d w a rd s, W abash, W hite, and G allatin C o u n ties; an area
152 a A B S T R A C T S .
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m iies farther west in Clay, Richland, an d W ayne Counties and the north-western corner of White C oun ty; and the south-central area in F a y ette, M arion, Clinton, W ashington, and Jefferson Counties.Of the forty-two sam ples analysed only four show m arked deviations from the general average, the others being sim ilar to O klahom a City crude oil, except th a t they are slightly more naphthenic and have a som ew hat higher sulphur content.
Inc luded in the report is a table listing the sam ples in order of increasing sulphur content, and from this it becomes apparent th at m ost of the high-sulphur oils are found in the o-roup of fields along the eastern border of the S ta te an d, further, th a t no low- sulphur oils are found in th at area. In fact, if a division is m ade betw een those having less than 0 1 8 % sulphur and those h aving 0-18% or m ore sulphur, none of the samples from the eastern area will fall into the first group. Sim ilarly all the sam ples from the area farther west in W ayne, R ichland an d Clay Counties will fall in the second group, and only six Of the rem aining sam ples from the south-central area will fall in the second group.
The question is raised as to whether a m ore extended su rv ey of Illinois crude oils would corroborate this apparent segregation of high-sulphur oils. H . B . M.
388.* Talco-Treating Methods Provide Fuel Economy and More Settling Time. G.
Weber. Oil Gas J . , 10.3.40, 39 (21), 34.— A description is given of various m ethods of water rem oval from the h eavy asphaltic Talco crude. T h e p articu lar problem in this field is the lack of gas, necessitating the purchase of fuel g a s for the treatin g of the crude. In general, the m axim um am ount of w ater is separated b y settling, and chemical treatm ent using 1 q t. to 25 q ts. for 1000 brl. oil is then carried out a t 120- 130° F . H ay-tanks consisting of baffles, excelsior section, an d h eaters are still used in the field, in addition to more modern m ethods. H e a t conservation is effected by preheating in sta ck an d return stream exch anges, utilization of non-condensible vent-gases from flumes and lease tan k s, and utilization of h eat in ex h au st gases of
pum ping engines. C. L . G.
Cracking.
389.* Improved Processes in Manufacture of Motor Fuels from Petroleum. G. Egloff.
Petrol. Engr, M idyear 1940, 11 (10), 21-26.— The prim ary function of cracking is to increase the quantity and im prove the qu ality of the gasoline th a t can be obtained from a crude. The success of this process m ay be gauged from the fact th a t, on cracking, an average yield of 45% is obtained from crude, com pared w ith 2 1% straight-run.
Further, an average octane num ber for cracked gasoline is 70, w hereas straight-runs are som etim es as low as 15.
In the ease of therm al cracking, a t tem peratures of 900-1100° F . an d 1000 lb./sq.
in. pressure, octane num bers average abou t 70 from charge sto ck s of gasoline, naphthas, or h eavy oils. To produce gasolines of higher octane num ber, catalytic cracking is available. C atalytic reform ing of gasoline or n ap h th as a t 950° F ., an d low pressure, m ay yield upw ards of 80% of 80-octane-num ber gasoline. T h e gases obtained as by-products are m uch richer in olefines th an those obtained from therm al cracking. These gases are converted into high-octane fuels either a t high tem peratures and pressures, or catalytically in the presence of phosphoric acid a t low tem perature and pressure. In this w ay the b utan e-b uten e fraction is cataly tically polym erized to yield iso-octenes, which are hydrogenated to iso-octanes.
iso -Octane is also m anufactured b y cataly tic alk ylation , ad ding butene to iso
butane a t 0-30° C. in the presence of 90-100% sulphuric acid. neo-H cxane, however, is best prepared b y therm al alkylation, using isobutane an d ethene a s charging stocks.
Another catalytic process of great im portance is isom erization, especially of butane to isobutane for use in the preparation of iso-octanes, but also generally of n- to isoparaffins.
The developm ent of cataly tic dehydrogenation of gaseous paraffins to olefines and hydrogen gives an im m ense source of raw m aterials for the sy nth esis of chemical derivatives, including synthetic rubber. B y cataly tic cyclization of the lower-boiling m em bers of paraffinic crudes, a new source of arom atics is av ailab le for the explosives industry.
A B S T R A C T S . 15 3 A than is possible under norm al cracking conditions, w ithout excessive coke form ation.
Polymerization and other side reactions increase the yield an d give more valuable of Cj and C
4
hydrocarbons which m u st be recycled through th e coils can be calculated.E a st 5 enezuelan n aphtha, W est T ex a s gasoline, an d a 50, 50 blend of M.C. an d P a.
gasoline gave yields on polyform ing in a simple once through unit of 77-84% of cracked distillate which when stabilized h ad an O .X . of 75-76. T y pical operating conditions were : b ack pressure on h eating elem ent 1000-1500 lb. per sq . in., tower pressure 300—100 lb., an d outlet tem perature from heater 1020-1125° F .
Two polyform u n its are equipped w ith c o k i n g drum s which handle the polyform ed residue, utilizing the w aste h eat in the furnace discharge, producing in addition gasoline and gas oil suitable for therm al c r a c k i n g production of water-w hite blends. B y m odifying conditions, a distillate of 80-84 O.X.
can be produced, which on acid treatm en t gives av iation of 77—79 O .X . requiring less than 3 c.c. lead to give 90 O .X ., an d an 80 O .X . av iation safety fuel. Such distillates contain high percentages of toluene and zylene, which can b e concentrated b v d is
tillation. C. L . G.
Hydrogenation.
391.* Destructive Hydrogenation Improves Product from Inferior Hydrocarbons.
R. Fussteig. Petrol. Engr, M arch 1940, 56-62.— In the petroleum industry, h ydro
genation im plies destru ctive h ydrogenation, w ith the intention of increasing the yield of high-grade gasoline from crude. I t is th u s pyrolysis followed im m ediately b y a d to bring about h ydrogenation before polym erization can tak e place.
E arly research w as hindered through the poisoning of cataly sts b y the hetero- elements present in petroleum , an d even w ith the m odem non-poisonable ty p es diffi
culties are still encountered. F o r in stan ce, w ith h eavy oils, except a t low throughput and partial pressure of p ro d u cts, the cataly st ten d s to be in activated b y the charge
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stock itself. To obviate this difficulty, the process is divided into two stages, liquid phase and vapour phase, each with its appropriate cataly st. In the first process higher molecular-weight hydrocarbons are split an d h ydrogenated to middle molecular- weight hydrocarbons, which, in turn, are split an d h ydrogenated in the vapour-phase process. In the hydrogenation of coal or charcoal a three-stage process m ust be employed for m axim um efficiency : first the oil-coal p a ste is hydrogenated in the
“ liquid ” phase to produce a h eavy oil, which is once m ore hydrogenated in the liquid phase and finally in the vapour phase.
Besides the true destructive hydrogenation processes, there are in existence com
bined hydrogen-addition-cracking sy stem s which differ in th a t sim ultaneous decom
position and hydrogenation take place in the former, w hereas in the latter the hydro
genation takes place after the rearrangem ent of the h ydrocarbon vapour.
The author concludes with descriptions of the flow-sheets of three existin g hydro- genation plants, two using h eavy oils as charge stock , an d the third coal.
392. Patent on Hydrogenation. H . B . K ipper. U .S .P . 2,224,603, 10.12.40. Appl.
17.8.39. D ehydrogenation an d oxidation of petroleum oils to produce so-called drying oils. The oils are selectively oxidized under agitation w ith nitric acid in the presence of an oxide of a m etallic elem ent, a s a cataly tic m aterial. Thereafter the oxidized oils are condensed with resins in the presence of so-called solid phosphoric
acid. H . B . M.