The quantitative relationships that we have found characterize the influence O f the principal reforming process variables on the rate of deactivation of the multimetallic catalyst KR-108. These relationships can be used in qualitative characterization of the behavior of other platinized reforming catalysts. They can provide a more specific approach to the selection of optimal service conditions for reforming catalysts, as well as a basis for the correct selection of the limits of change in the process conditions when designing new catalytic reformers. LITERATURE CITED 1.

2. 3. 4. 5. 6. 7. 8.

.

G. H. Froment, Proceedings of 4th International Congress on Catalysis, No. I, 10-31 (1976). R. Bacaud, G. Barbier, G. Blanchard, et al., J. Chim. Phys., 77, No. 5, 387-392 (1980). B. G. Cooper and D. L. Trimm, in: Catalyst Deactivation, Elsevier, New York (1980), pp. 63-71. L. M. Parera, N. S. Figoli, E. L. Jablonski, et al., in: Catalyst Deactivation, Elsevier, New York (1980), pp. 571-576. Yu. M. Zhorov, G. M. Panchenko, and Yu. N. Kartashov, Kinet. Katal., 21, No. 3, 776780 (1980). S. R. Tennison, Chem. Br., 17, No. ii, 536-539 (1981). G. B. Rabinovich, Yu. P. Borisevich, R. A. Bakulin, et al., Katal. Konversiya Uglevodorodov (Kiev), No. 6, 24-26 (1981). E. A. Shkuratova, A. P. Fedorov, N. P. Mel'nikova, et al., Production and Separation of Products from Petrochemical Synthesis [in Russian], Krasnodarskoe Knizhnoe Izd., Krasnodar (1975), pp. 55-64. G. N. Maslyanskii, B. B. Zharkov, A. P. Fedorov, et al., Khim. Tekhnol. Topl. Masel, No. I0, 5-14 (1979).

INCREASING THE DEGREE OF SULFONATION OF PETROLEUM OILS IN OIL-SOLUBLE SULFONATE PRODUCTION O. S. Kachmar, A. N. Bodan, B. V. Kachmar, and P. D. Kopchik

UDC 665.767.1

In the sulfonatlon of petroleum stocks to produce oil-soluble sulfonates, greater degrees of sulfonation of the oil are desirable because of two factors: the reduced consumption of the petroleum stock to obtain sulfonic acids in manufacturing the commercial product, and the reduced consumption of the sulfonating agent (oleum) when using the sulfonated neutral oil in the subsequent production of white oils [i, 2]. Sodium sulfonate of the quality required for the production of lubricating/cooling fluids can be obtained by comparatively mild sulfonation of the oil in each stage. The sulfonated oil, after separating the acid tar, should contain i0-13% sulfonic acids. Here, the content of aromatic hydrocarbons after the second sulfonation stage remains quite high, 7-18%, depending on the content of aromatics in the original stock. In order to determine the feasibility of efficient use of the remaining alkylaromatic hydrocarbons, laboratory sulfonation studies were perfarmed on a neutral oil obtained after two-stage pilot-plant sulfonation of oils from various crudes. The original stocks were viscous distillate oils produced at the "Kuibyshevnefteorgsintez" Industrial Association from mixed Volga medium-sulfur Romashkino-type crudes and West Siberian crudes, and at the Volgograd Petroleum Refinery from low-sulfur crudes of the Zhirnovsk and Korobki type. The contents of aromatic hydrocarbons in the original oils were 36.2% and 23.7% by weight, respectively; after two-stage sulfonation, the respective aromatic contents were 17.6% and 6.5% by weight. All-Union Scientific-Research and Design Industry of the Petroleum Refining and Petrochemical Industry (VNllPKneftekhim). Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 9, pp. 17-18, September, 1984.

0009-3092/84/0910-0435508.50

9 1985 Plenum Publlshing Corporation

435

TABLE 1 t__

Oil f r o m , Kuibvshevneffrom Volgggrad teorgsintez" Indbstrial Astroieum P~finer y ~soci~tion after indicated after indicated stage stage of sulfonation ,of sulfonation

pOeil

Index

=

8 1

8

~o

/

Yield, wt. ~o on originaloil for sulfonation sulfonatedoil acid tar Characteristicsof sulfonat~d oil total acid number, : m ~ KOH/g su[fonic acid content, wu qo Yield. wt. ~0 on ori@nal

~6,6 11,2

]91

17,3

4~8

.8,2

l0,5

stock

oil-solublesulfonieacids in s t a g e total acid tar in stag-e total ., Consumption oqf o.rlginal ofi per tog or suuomc aclos,Kg ha stage total Process selectivity, quantity of sulfonie acids per kg. o f acid tar, kg in stage total

60 :54

1;3 t~;7

73 ~39 67 6,5

77,7

0,8~ 0;32: 0;6o O, 64

Note. First and second sulfonation stages were performed in pilot unitj third and fourth stages in laboratory unit. TABLE 2 Neutral oil :original ~

Indexes

0,4:1

1:1

58,8/--

69,1/-29,2/--

25,4/--

19,6/17,7 9,4/7,7

17,0/12;0 8,7/7,6

8,4/7,19 10,1/8,5

7,7/6,8 12,5/I 1,4

12,0/lO,O

8,4/5,3 8,4/13,7

I0,7/7,1

12,4/8,6 12,4/21,0

i0,I/6,4 10,1/16,5 11,9/7,3

17,4/12,0 17,4/29,4 9,3/5,6

24,o/15,6

0:1

Contents of hydrocarbons in sulfonafion feed (blend),wt. 9o paraffim:.~ naphthenes aromatics

ratio-

!

38,9/--

73,2/~-

Characteristicsof sulfonatedoli total acid number, mg K O H / ~ content of sulfonieacids,wt. v/o Yield, wt. 9o,on sulfonation feed 9 oil-soluble sulfonic acid8 acid tar Yield. wt. 9o on originalfeed oil-sohablesulfomc acids m s~age 9 " 9 " total . = acid tar in stage ~ total =-~ Consumption of oil per kg of suifonic . acids, kg ~ ,. ' Not e, First value to second stage,

refers

to

first

10,7/17,8

stage,

second

13,7/9,7 7,0/6,1

6,2/5,5

24,0/39,6

8,1/4,8

value

The sulfonation was performed under conditions identical to those used in the firstand second-stage sulfonations. The inputs of oil and sulfonating gas were kept the same, as was the sulfonation temperature. The yields and quality of the products from the sulfonation are given in Table I. With increasing degree of sulfonation of the stock from "Kulbyshevnefteorgsintez" Industrial Association, the content of sulfonic acids obtained in the

436

TABLE 3 Hydrocarbon =rouo cdns~rnpfion5f otis, wt.v/o . ,

: .....

Neutral oil

Multistage sulfonation After indicated | sulfonation stag~ second [ 81,3 17,6 ~third | 87,3 11,8 fourth / 92,6 6,3

1,1 0,9 1,1

Sulfonafion with neutral oil recycle

Ra~o of neural oil to original oil - -o,4il

hi

90,8 93,1

8,5 6,1

0,7 0,8

Note. The original oil was obtained at the "Kuibyshevnefteorgsintez" Industrial Association. third stage dropped to 7.7%, and in the fourth stage to 2,6%. This drop is sulfonic acid yield is still greater when recalculated to yields on the original stock (3.8% and 1%, respectively). The yield of acid tar also decreased with progressive sulfonation, but the decrease was less pronounced than in the case of the sulfonic acids, and hence the net result was a decrease in selectivity in the third and fourth stages of sulfonation. Upon going from the first stage to the second, the process selectivity increased, because of the improvement in the composition of the aromatic hydrocarbons in the second-stage feed (smaller content of condensed structure). As the sulfonation progressed, the product quality changed, particularly that of the acid tar, which showed an increasing total acid number from stage to stage (134, 177, 212, and 383 mg KOH/g) and an increasing content of sulfuric acid (7.5%, 10%, 13%, and 28% by weight). Similar relationships were obtained in the progressive sulfonation of the oil from Volgograd Petroleum Refinery. With a constant consumption of sulfonating agent (SOs), its oxidizing action increased as the content of aromatic hydrocarbons decreased in the third and fourth stages, as indicated by the increase in the relative yield of acid tar in the third stage and particularly in the fourth stage and the increased content of free sulfuric acid in the tar. These resul~s were obtained in spite of the uniformity of the sulfonation feedstock with respect to the structure of the aromatic hydrocarbons and the continuous increase in the relative amount of alkylaromatic hydrocarbons in the total aromatics, giving a minimum quantity of acid tar ~oil-insoluble sulfonic acids). This phenomenon can be explained by the increase, fromstage to stage, in the specific consumption of sulfonating agent relative to the content of aromatic hydrocarbons in the feed. Thus, in order to increase the process selectivity and utilize the equipment more efficiently, the sulfonation feedstock should be selected to have the highest possible content of alkylaromatic hydrocarbons, and the process itself should not cut deeply into these alkylaromatics. As the sulfonation progresses, these process indexes become poorer: however, the aromatic hydrocarbons in the original feed arebetter utilized, and there is an improvement in the quality of the neutral oil as a starting material for white oil production. These same ends can be achieved by recycling part of the neutral oil from the second stage of sulfonation back to the first stage [3]. We have carried out the sulfonation of a mixture of the oil from the "Kuibyshevnefteorgsintez" Industrial Association and the neutral oil after the second stage, with recircu!ation of the latter. The incorporation of the neu-

437

tral oil in the sulfonatlon feed has very little effect on the process results (Table 2). The product yields and their quality remain essentially at the level of the analogous indexes obtained in the sulfonation of the original oils. However, a trend is observed toward a decreasing content of sulfonic acids in the sulfonated oil as the amount of neutral oil in the feed blend is increased. The differences can be seen more clearly when the yields of sulfonic acids and acid tar are referred to the original feed. lhus, with either method of increasing the process selectivity, we find an increase in the relative yield of acid tar as the degree of utilization of the aromatic hydrocarbons of the feed is increased. However, when the sulfonation is performed on a blend with recycled neutral oil from the second stage, this trend is manifested to a greater degree (see Tables 1 and 2). The quality of the neutral oil that is obtained is approximately the same in the two cases (Table 3). The content of paraffins + naphthenes is ~93%, aromatics 5-6%. Further sulfonation is inadvisable, owing to the low content (approximately 2% of sulfonic acids in the sulfonated oil, which amounts to less than 1% relative to the original feed. Thus, a fuller utilization of the aromatic hydrocarbons of the feed, i.e., a decrease in the specific consumption of feed relative to the sulfonic acids produced, can be achieved by increasing the degree of sulfonation (in three stages) or by recycling the neutral oil from the first stage. Preference should be given to the three-stage sulfonation, particularly in the case of original feeds containing more than 35% aromatic hydrocarbons. The more thorough sulfonation leads to decreases in the process selectivity and in the efficiency of equipment operation. LITERATURE CITED i. 2. 3.

438

V . A . Potanina, E. N. Marcheva, Sh. K. Bogdanov, et al., Khim. Tekhnol. Topl. Masel, No. i, 47-49 (1981). A . S . Zhurba, V. M. Bludilin, V. N. Antonov, et al., Khim. Tekhnol. Topl. Masel, No. 5, 13-15 (1981). USSR Inventor's Certificate 612,950.