I N D U S T R I A L A N D ENGINEERING CHEMISTRY
804
Vol. 23. No. 7
Effect of Properties of Petroleum Wash Oil in Removal of Light Oil from Coke-Oven Gas’ H. R. M a t h i a s TECHNICAL DIVISION,STANDARD OIL COMPANY(INDIANA),910 SOUTHMICHIGAN AvE., CHICAGO,ILL.
*
BSORBENT o i l ” i s the general term for petroleum oil which is used in scrubbing towers for r e m o v i n g the light oil from coke-oven gas. The industry also commonly designates the product as “wash
“A
Oil.”
Troubles commonly encountered in t h e use of a b sorbent oils a r e described a n d t e s t s ordinarily m a d e o n these oils are considered f r o m the s t a n d p o i n t of t h e i r relevancy to service r e q u i r e m e n t s a n d t h e i r bearing on sludge a n d deposit troubles. T e s t s of value a r e listed, along w i t h a new t e s t for evaluating the stability of wash oils toward oxidation. Those f o u n d to be of little or no value include the much discussed “olefin content.” Evidence is given t o show that “olefins” a r e not responsible for distillation losses or sludging in decanters, the l a t t e r being eliminated by m a i n t a i n i n g specific gravity, viscosity, a n d emulsion test as low as possible. Scrubbing-tower deposits a r e d u e primarily to coal derivatives held in t h e oil, altered by oxidation a n d polymerization. T h e use of m o r e stable oils seems t o reduce the r a t e of f o r m a t i o n of deposits in towers. A short laboratory absorption t e s t indicates little difference in light-oil yield a m o n g oils varying considerably in properties. T h e results a r e s o m e w h a t i n favor of the use .of oils of higher specific gravity, viscosity, a n d sulfuric acid absorption, a l t h o u g h such oils generally give sludging troubles. Hence absorbing efficiency is usually of secondary i m p o r t a n c e in choosing wash oils.
Briefly, the process of using absorbent oil consists in passing the cold oil over wood grids, where it comes into intimate contact with the entering gas, the direction of flow being countercurrent. The light oil and other materials in the gas, such as tar fog and fine dust particles which have escaped the amm o n i a s c r u b b e r s and gas washers, are removed by the absorbent oil, which is subsequently steam-distilled to remove and recover the light oil. The debenzolized absorbent oil passes from the steam still to decanters where the water is separated, thence through the coolers, and back into circulation in the scrubbing towers, completing the cycle. During this process the oil is subject to a wide range of temperature, and for some time hot oil is exposed to the oxidizing influence of air. I n the use of absorbent oil various troubles are encountered, the most disturbing of which are:
(1) Too high content of absorbent oil in the steam distillate, which represents loss of oil from the system and is oftentimes a source of trouble in subsequent refining of the light oil. (2) An emulsion of oil and water (sludge) in the decanters and coolers. This emulsion ordinarily is discarded and represents loss of oil from the system. I n extreme cases it appears in such quantities as to interfere seriously with the desired rate of circulation, necessitating considerable labor for removal from decanters and coolers. (3) Deposit of a bituminous material in the scrubbing towers which in time blocks the passages, usually making necessary final dismantling and hand cleaning of the grids, a very expensive, time-consuming operation.
The tendency has been to ascribe these troubles to high olefin content of the oil as purchased. The present investigation was made for the purpose of determining the truth or error in this assumption and to find out the actual contributing factors with possible remedies. Methods of Test
Each oil subsequently subjected to plant runs was first examined for its physical and chemical properties as ordinarily outlined by specification test methods. Each test was sub1 Received
February 21, 1931.
Presented before the Division of
Gas and Fuel Chemistry at the 81st Meeting of the American Chemical
Society, Indianapolis, Ind., March 30 to April 3, 1931.
j e c t e d to s c r u t i n y to determine its relevancy to the actual service requirements of an absorbent oil. It is a common experience to find included in specifications tests which h a v e l i t t l e , if any, bearing on the use of the oil or by which l i t t l e c a n be learned in advance of its probable behavior in the circulating system. The following tests, c o m m o n l y f o u n d in specifications, are considered:
SPECIFIC GRAVITY-The determination is made by pycnometer or specific-gravity b o t t l e a n d c o m p a r e d with water a t 15.5” C. The usual requirements call for as low a specific gravity as possible, b u t no higher than 0.875 a t 15.5”C. Inasmuch as the oil must separate from water readily in use, the l o w e s t p o s s i b l e specific gravity concomitant with other properties is desirable. V1scos1~y-S~eci f i c a t i o n methods usuall; refer t o the Saybolt A viscometer. Inasmuch as the Saybolt Universal viscometer is standard in the petroleum industry, specifications based on it are more desirable. On this basis a variation from 185 to 65 seconds Saybolt Universal a t 100” F. (37.8” C.) maximum is found in specifications. Inasmuch as an oil of low viscosity separates from water faster and more completely than a n oil of high viscosity, other things being equal, it is apparent that some specifications are far too generous in the maximum limit. This test is of value for inspection of an absorbent oil. Loss ON STEAMDISTILLATION-Amaximum loss of 2 per cent is allowable upon steam-distilling 500 cc. of oil with 500 grams of steam a t atmospheric pressure, no flame being used on the flask. Experience with its use has demonstrated that results check within 0.5 per cent of the total 2.0 per cent loss allowed. Owing to difficulties of manipulation, the effect of technic, and differences in atmospheric temperature and pressure, the test is not reproducible within closer limits. Inasmuch as a dry distillation for initial boiling point is usually performed, i t seems preferable to the steam-distillation test, although there is no serious objection to using the latter provided its limitations are considered . EMULSIFICATION ON STEAM DISTILLATION-The specifications state that no permanent emulsion or “rag” must lie between the volatilized oil and water layers after steam distillation. This test is an indication of the separating quality of the fresh oil from water in the decanters. The oil in use picks up foreign materials from the gas, which greatly affect its separating properties. This indicates that the test is of lictle value when applied to the fresh oil, except to insure that the initial demulsibility is as high as possible. This test amounts to a practical duplication of the emulsion test given below, as far as determining the quality of the oil is concerned, and is therefore unnecessary. EMULSIONTEST-one hundred cubic centimeters of fresh oil are shaken vigorously for 20 minutes with 100 cc. of distilled water in a stoppered 200-cc. graduated cylinder, 20 to 22 cm. in length, which has previously been rendered chemically clean. Most specifications are rather indefinite in disclosing a method for this test. I t is found that the above method, when followed carefully, will give consistent, reproducible results. Inasmuch as this test is performed on the fresh oil, it a t first seems open to
July, 1931
INDUSTRIAL AND ENGINEERING CHEMISTRY
the same objection as the preceding test. However, by its use it is possible t o eliminate an oil which would give trouble from emulsification in the decanters. Most specifications require a t least 95 per cent separation l?,minutes, with no formation of permanent emulsion or rag. INITIAL BOILIXGPOINT-The temperature of the oil is read when the first drop falls during an otherwise A. S.T. M. 100-cc. dry distillation. All specifications place a minimum of 285" c. (545' F.) initial boiling point. This test, as previously mentioned, is preferable t o the test for loss on steam distillation, being quicker and easier to run. An oil with an initial boiling point below 285' C. will usually show a loss on steam distillation greater than 2 per cent. FREEZING TEST-This test should be made according t o the A. S.T. M. method for the pour test. The specifications are usually very indefinite, refemng to thickening of the: oil, which might be construed t o mean an increase in viscosity to which all oils are subject upon cooling. Inasmuch as the oil is exposed a t times to low temperatures, a maximum A. S. T. M. pour test of 5 " C. seems a logical requirement. OLEFINs-In the results appearing in this paper, "olefins" are reported as the per cent loss to 100 per cent sulfuric acid a t 0" C. Considerable variation is found in methods for determining olefins, most tests being made a t room temperature and a t higher acid concentrations, which result in considerably greater absorption. Concentrated sulfuric acid removes other substances from petroleum oils as well as olefins, particularly at room temperature. The difficulty of obtaining reproducible results and the lack of uniformity in test methods render this test of insufficient accuracy for specification purposes. As will be developed, olefins have little t o do with the quality of a n absorbent oil; hence this item should be eliminated from specifications. COLOR-color of the absorbent oil can only assume importance in relation to the color of the light-oil distillate, which always contains some wash oil, Inasmuch as this crude product is treated and distilled to secure commercial products, the influence of color of the wash oil on the finished products is nil. It is inconceivable that a light color is more than an incidental property of a good oil. Color has no place in consideration of the necessary properties of an absorbent oil. BOILINGRANGE-This is often set a t 60" (140" F.),between the initial and final boiling points or as low as possible. With the initial boiling point already set a t a certain minimum, this test is unnecessary except to eliminate too heavy an oil. This latter point is cared for in the viscosity specification. OXIDATION SLUDGE-This test was devised in order to estimate accurately the tendency of a wash oil to form deposits as the result of oxidation of unstable compounds. It seeks to approximate service conditions under which oxidation takes place. Ten grams of oil are weighed into a 50-cc. beaker and placed in a constant-temperature oven for 5 hours a t 162.8" C. (325" F.) At the end of this period the oil is taken up in A. S T. M. precipitation naphtha. The insoluble residue, representing oxidized oil, gums, and resins, is filtered into a Gooch crucible and washed with precipitation naphtha. The crucible is dried for 2 hours in a n oven a t 121.1-135' C. (250-275' F.). The residue is reported as "oxidation sludge" and expressed in per cent. When performing this test on debenzolized oils, it is necessary to determine the naphtha-insoluble material present before oxidation. This is termed "original sludge" and is determined by dissolving 10 grams of oil in precipitation naphtha, filtering and washing the residue, and reporting in per cent as above. The original sludge must be known before interpretations can be made of results on oxidation sludge, because of the much greater instability toward oxidation of such material.
:!
c.
Loss on Distillation
A comparison of the boiling points of olefin and paraffin hydrocarbons is sufficient proof that there is no preferential distillation of olefins, as the corresponding paraffins and olefins are very close together. Absorption tests with sulfuric acid of the residue left upon redistilling the steam distillate demonstrate this fact, for the amount of absorption is of the same order as that found with the fresh oil. High steam-distillation losses are doubtless due to the use of an oil of too low initial boiling point, and not to presence of olefins. Sludge in Decanters
Sludge occurring in decanters, upon examination in several cases, proved to contain about 25 per cent oil, the remainder being water and a small amount of finely divided solid matter.
805
The presenceof olefins in the fresh oil, as previously mentioned, has been thought to promote the formation of this emulsion. The fact that filtration will break this sludge seemed to indicate otherwise-i. e., that finely divided solid matter was acting as an emulsifier. It is well known that absorbent oils thicken appreciably in use. Ullmann and collaborators, in a paper on the thickening of wash oil ( I ) , disclosed interesting findings with respect to sulfur content of the gas and oil. The writer leans strongly to the view that the thickening is mechanical rather than chemical (action of sulfur-bearing gases) and represents solution by the wash oil of materials of high specific gravity and viscosity from the gas, resulting in an increase of both properties in the wash oil. In the belief that sludging might be reduced by the use of an oil of as low viscosity and specific gravity as possible, with corresponding better separating quality so that the effect of the contaminating materials on viscosity and specific gravity might be minimized, the data in Table I were obtained after long plant runs. Table I-Decanter
Sludge Test Loss ON
STEAMEMULSION TEST H~SOI ABSORBEXT VISDISTIL- SepaABSORPOIL COSITY SP. GR. I. B. P. LATION ration Time TION S.e c~. . O C. P .'Z % ' Min Sec.-Fresh 1 55 0.8762 305 581 1.8 100 7 42 23.0 De6enzolized 1 65 0.8923 325 617 0.9 100 20 37 38.3 Fresh 2 44 0.8462 290 554 2.0 100 1 33 22.0 Debenzolized 2 52 0.8630 . . ... ... 100 3 00 30.0 Fresh 3 46 0,8285 . . 1.0 100 2 00 7.0 Debenzolized 3 59 0,8571 315.6 800 ... 100 3 30 15.0 ,I
,I
~~
,I
Debenzolized oil 1 gave repeated trouble from sludging. The viscosity had increased from 55 to 65, specific gravity to 0.8923, demulsibility had decreased markedly, and the solubility in 100 per cent sulfuric acid had increased 15.3 per cent a t 0' C. The amount of sludge discarded weekly was equivalent to a loss of 1000 gallons (3785 liters) of wash oil. Plans had been made to purchase a filter press so that this oil could be recovered. However, by changing to oil 2, which was considerably lower in specific gravity and viscosity, although of the same olefin content as oil 1, sludging was entirely eliminated. Although during the use of oil 2 specific gravity and viscosity were increased, causing a falling off in demulsibility, and olefin content increased by 8 per cent, sludge no longer appeared. Since the olefin content of the fresh oil was the same in both cases, the improvement is probably attributable to lower resultant specific gravity and viscosity, with corresponding better demulsibility. Oil 3, now in use, of approximately the same viscosity as oil 2 but a little lower in specific gravity and considerably lower in original olefin content, is giving results equivalent to those obtained with oil 2. The conclusion is reached that elimination of sludge does not depend upon olefin content, but is secured by maintaining as low specific gravity and viscosity as possible. This supports the belief that the direct cause of sludge is finely divided solid matter, promoting the formation of an emulsion when the specific gravity of the oil gets too close to that of water and the viscosity is relatively high. At the time the samples analyzed above were secured, each oil had been in use about 1 year, with the exception of debenzolized oil 1,which had been in use about 2 years. This longer time of service for oil 1 is doubtless responsible for the higher percentage of olefins. I n all cases the sulfuric acid absorption increases with use. Quoting from a report made by the chemist of a large coke plant: In comparing olefin content of oil before and after use, we find that on August 10 a spot sample of debenzolized oil from the system showed 26 per cent olefins, which was higher than
INDUSTRIAL AND E-VGINEERING CHEJfIXTRY
806
the average olefin content of the oil placed in service a t that time, indicating that olefins must be picked up from gas. Again on August 18, 24-hour samples of debenzolized and benzolized oils gave 27 and 27.5 per cent, respectively. On August 31 and September 1, debenzolized showed 33.3 and 33.0 per cent, respectively. On December 8, debenzolized showed 38.3 per cent loss to sulfuric.
A survey of oils in use a t various plants indicates that loss to 100 per cent sulfuric acid at 0” C. (olefin content) increases by an average of 7 to 9 per cent after about 1 year’s use. The results of this survey are given in Table 11. Table 11-Investigation
of Absorbent Oils
Vol. 23, No. 7
recovered per ton of coal were calculated and plotted against the temperatures noted on dry distillation, as in Figure 1. The curves for the different oils are very close up to 150” C., a t which temperature most of the light oil is probably over. It is apparent that very little difference exists in the absorbing power of the oils studied, such differences being somewhat in favor of higher yields with oils of higher specific gravity, viscosity, and loss to sulfuric acid. According to Raoult’s law, the opposite would be expected, for the heavier oils are of greater average molecular weight. Deviations from Raoult’s law are doubtless responsible for this apparent contradiction, as previously suggested by Wilson and Wylde (2):
LOSS ON
On
VISCOSITY
SP. GR.
Sec.
O
I. B. P. C. O P.
STEAMEMULSION TEST HsSOc DISTIL- SepaABSORPLATION ration Time TION
%
Yo Min. Sec.
%
5
00 30 00 30
18.0 10.5 7.0
00 00 30 00
27.0 17.0 15.0 36.5
FRESH OILS
A B 3
c
56 51 45 62
0.8745 0.8591 0.8285 0.8418
304.4 315
580 599
3ii.8
595
...
1.6 0.8 1.0 0.8
__
DF.BRN7.OLIZED ~~~~
A B C 3
65 69 59 87
0.8927 0.8767 0.8571 0.9076
198.9 287.8 348.9 165.6
~~~~
390 550 600 380
100 100 100 100
OILS . ~
... .., ... ...
4 2 9
~
16 98 100 5
8.0
_
10 10 3 10
Oil C has been in use for a long time without changing, which probably explains its great increase in olefins, viscosity, and specific gravity. Debenzolized oils B and 3, while practically the same in olefin content, show a marked d s e r ence in emulsion test. This is explainable by the lower viscosity and specific gravity of debenzolized oil 3, and affords additional evidence that olefin content is not a measure of separating ability. Oils A, B, and 3, which have been in use about the same length of time, show nearly the same increase in olefin content. While increase of o l e h content of debenzolized oils is indicative of increase in specific gravity and viscosity and corresponding decrease in demulsibility, the relation is by no means quantitative and may lead to erroneous deductions if an attempt is made to estimate the sludging tendency of the oil.
As far as deviation from Raoult’s law a t the lower concentrations are concerned, the four kinds (classes) of oil may be arranged in the following general order of increasing tendency to absorb, for a given molecular weight: California, asphaltbase, paraffin-base, and castor. It will be noted, however, that this is also precisely the order of increasing molecular weight for a given viscosity, and since, if Raoult’s law held precisely, the oils of higher molecular weight would absorb less solvent, the two effects tend t o neutralize one another to a surprising extent, especially for the mineral oils. The same tendency was observed in the case of the gas-absorbent oils of different molecular weight but similar source [as in this case]the deviation from Raoult’s law almost exactly counterbalanced differences in molecular weight.
REL RTlVE RBORBINS POWER OFOILS
FRsk
04 NO.1 Fresh
O/l
“0”
Fresh Oil NO.2
Comparison of Oils for Absorption
Mutual solubility of hydrocarbons is affected considerably by the relative nature of the solvent and solute. It is logical to assume that an oil containing a high percentage of unsaturates will dissolve a larger amount of benzol than an oil containing less. To test the validity of this assumption, an absorption test was arranged. Although the number of runs was not sufficient to form the basis of definite conclusions, the results give indication that this assumption is probably justified. Detarred gas was passed through a bubble tube into samples of fresh oil 1,debenzolized oil 1, fresh oil 2 (Table I),and fresh oil D. Fresh oil D is the distillate from which fresh oil 2 was prepared as a middle fraction by redistillation. Tests on the oils are repeated in Table I11for comparative purposes. Table 111-Oils Used in Absorption Test LOSS ON
On
vxsCOSITY
Sec. 55 Fresh 1 Debenzolized 1 65 Fresh 2 44 46 Fresh D
SP. GR.
0.8762 0.8923 0.8462 0.8484
STEAM EMULSION TEST HIS04 DISTIL-SeparaABSORPI. B. P. LATION tion Time TION C. O F. ?A ?A Min. SCC. % 7 42 2310 100 1,’s 305 581 100 20 37 38.3 0.9 326 617 1 33 22.0 100 2.0 290 554 100 10 00 22.1 4.6 271 520
After gas had been passed through each oil for the same length of time, the benzolized oils were steam-distilled and the volatile fractions thus secured subjected to a dry distillation to separate the light oil from absorbent oil carried over. Assuming 10,750 cubic feet of gas per ton of coal, the gallons
lm
dy)
D y e s Cenlnigmde
-
6OILING RANGE RECOVERED LIGHT OIL Figure 1
Indeed in some ways the most striking fact brought out by the whole investigation is the comparatively small difference in per cent by weight or volume of a given solvent [benzene among those studied] absorbed under specified conditions by widely different kinds of hydrocarbon oils. This conclusion does not apply t o other non-volatile oils containing oxygen, such as glycerides, cresols, etc.
Because of sludging difficulties usually experienced when specific gravity is close to that of water and viscosity is high, it is undesirable to use an oil of too high specific gravity and viscosity. For this reason absorbing efficiency is usually of secondary importance. Deposit in Scrubbing Towers
Within the last year opportunity has been afforded to study the facts relating to the formation of a pitchlike deposit in the scrubbing towers. The accumulation of this deposit
I N D USTRIAL AA-D ESGINEERING CHEMISTRY
July, 1931
seriously affects the efficiency of the towers, making necessary a final dismantling and cleaning. It has been thought that oils of greater stability toward oxidation and polymerization than some now in use might eliminate the trouble. The use of a stable oil would undoubtedly reduce deposits of oxidized and polymerized petroleum oil, but the author believes that materials picked up from the gas are more responsible for the formation of these deposits. I n order to determine the relative stability of various oils, analyses were made of samples of fresh and debenzolized oils after months of use, as well as of a typical deposit. It was surmised that the per cent loss to sulfuric acid (olefin content) might prove to be an index of stability toward oxidation and polymerization, although the method of test is open to inaccuracies. Olefin content was therefore compared ,with the results of the oxidation sludge test described earlier, in order to determine the extent of agreement between the two tests. Table IV-Stability LOSS TO
OIL
HzS04
of Absorbent Oils OXIDATION SLUDGE
%
3 C
M P
LQ
OILS
18.0 10.5 7.0 8.0 16.0 14.0
8.0
DBBBNZOLIZED
A B
SLUDGE
%
% FRESH
A B
ORIGINAL
27.0 17.0 3 15.0 C 36.5 La 11.0 4 Oil subjected to a short laboratory 21 days.
0.040 0.034 0.020 0.005 0.027 0.018
0.007 ons 1.400 1.200 0.890
... ... ... ... .,. ... ... 0.170 0.070 0.040
... ...
0.760 0.022 absorption of detarred
gas
for
The significance of the item “original sludge” has been discussed. A study of Table IV shows that in general a high olefin content is indicative of relatively poor stability and greater tendency to form deposits as measured by the oxidation sludge test. Inspection shows, however, that olefin content is an untrustworthy index, as can be seen by comparing results on fresh oils A and B. Oil B shows 15 per cent less oxidation sludge than oil A, but 44.67 per cent less olefins. Likewise, fresh oil C, although of practically the same olefin content as fresh oil 3, shows only one-fourth as much oxidation sludge. Comparison of the olefin content and oxidation sludge of debenzolized oils discloses even greater disagreement. It is evident that olefin content is a rough but unreliable measure of sludging tendency. The large increase of oxidation sludge in the debenzolized oils is undoubtedly the result of lower stability of the coal derivatives picked up by the oil. Debenzolized oil A showed 1.400 per cent oxidation sludge; the fresh oil showed 0.040 per cent oxidation sludge. The very great increase is doubtless attributable to alteration of the 0.170 per cent naphthainsoluble matter (original sludge), most of which is of coal-tar nature, which the oil has removed from the gas. On the basis of this information, it is logical to believe that a scrubbing-tower deposit consists largely of altered coal derivatives, and that the original stability of the oil plays a relatively small part. A long-time test is now in progress, however, on oil P, replacing oil B. Oil B gave great trouble with deposits. After about 6 months’ use of oil P, back pressure has not yet increased, indicating that deposits are not building up: As far as is known, the conditions of use are identical. It is possible that deposits from the oil act as binders for the tarry material. Further results from the plant test available within the next 6 months may throw more light on this phase of the subject. Examination of a typical deposit secured from a scrubbing
807
tower indicates that the prime source is contaminants from the gas. About 30 per cent of the deposit consists of siliceous material and cokelike particles, insoluble in benzol. The bituminous portion, representing about 70 per cent, which was soluble in benzol, is apparently a mixture of coal tar and petroleum bitumens (specific gravity by pycnometer, 0.9159). This bitumen has no definite softening point, burning to a very voluminous carbonaceous ash when an attempt is made to melt it. No attempt was made toward identification of any of the constituents. Conclusions 1-High distillation losses are not due to olefins in the fresh oil, but rather to the use of oils of too low initial boiling point. 2-Olefins are not responsible for sludging in decanters. Sludge is eliminated by maintaining specific gravity, viscosity, and emulsion test as low as possible. 3-Olefins and oils of high specific gravity and viscosity may possibly be of some benefit in increasing absorption yield of light oil. Oils of high specific gravity and viscosity, however, are undesirable because of the sludging troubles usually encountered. &Deposits in scrubbing towers are due primarily to coal derivatives held in the oil, altered by oxidation and polymerization. Use of more stable oils may reduce the rate of formation of such deposits. 5-An oxidation-sludge test for estimating the relative stability of oils gives more accurate results than inferences drawn from olefm content. 6-The desirable tests for determining the quality of an absorbent oil are specific gravity, viscosity, loss on steam distillation (initial boiling point preferable), emulsion test, initial boiling point, pour test, and oxidation sludge. 7-Unnecessary tests, which are of little or no value for evaluating suitability of absorbent oils, are emulsification on steam distillation, color, boiling range, and “olefins.” Acknowledgment The author is grateful for assistance, criticism, and cooperation in experimental work received from R. B. Chamberlin, chief chemist, Interlake Iron Corporation, and C. W. C. Page, chief chemist, St. Louis Gas and Coke Company, and to other operators of by-product coke plants who kindly furnished samples for this work. Literature Cited (1) Ullmann, Chamberlin, Simmons, and Thorpe, IND. EXG.CHEM.,21, 313 (1929). (2) Wilson and Wylde, I b i d . , 16, 801 (1923).
American Toiletries Introduced in Rumania Though an appreciable demand and a distinct preference for foreign-made toilet preparations characterized the Rumanian market during recent years, governmental restrictions militated against the importation of such products into Rumania and nurtured the domestic toilet preparations industry. This situation, however, has now been considerably altered, according to our consul a t Bucharest. A substantial reduction in import duties, bringing down the rate on face powders to one-fifth of the former tariff, on creams and other cosmetics one-third, on lotions nearly one-half, and on perfume nearly one-third, has made possible the importation of these products into that country. Widespread advertising in newspapers and magazines has contributed to the increased sales of particular makes of cosmetics in Rumania, Newspaper and magazine advertising has shown a decided trend toward American forms of presentation. This is particularly noticeable in the press of Bucharest, which has a wide circulation throughout the country and which includes newspapers with 14 pages, of which more than half the space is devoted to advertising.
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