tire.

Thus, efforts in improving the SIM additive manufacturing technology should be directed toward removing the polybutenes, which can then be reused in synthesizing the alkenylsuccinimide additive SIM.
LITERATURE CITED
i.
2.
3.
4.

Yu. N. Shekhner, S. ~. Krein, and L. N. Teterina, Oil-Soluble Surfactants [in Russian],

Khimiya, Moscow (1978), p. 166.
T. D. Popovich, O. L. Glavati, and T. P. Pliev, Neftekhimiya, 16, No. 5, 773-776 (1976).
G. P. Gashko, O. L. Glavati, Ya. E. Garun, at al., Tr. Vses. Ob'edin. Neftekhim., No.
ii, 35-58 (1976).
A. V. Fokin, M. V. Pospelov, Yu. N. Shekhter, et al., Khim. Tekhnol. Topl. Masel, No. 8,
25-27 [year not given].

HYDRODEALKYLATION OF TOLUENE USING HYDROGEN-RICH REFORMER GAS

V. I. Golubyatnikov, V. M. Kapustin,
and A. I. Lugovskoi

UDC 665.654

A combination unit for benzene production has been put into service at the Ryazan' refinery. This unit consists of three main sections (see Fig. la): hydrodealkylation, cryogenic treatment of hydrogen-rich gas, and hydrogen production. Since the refinery has extensive reforming facilities, hydrogen-rich gas (HRG) is produced in considerable excess over
the amount required by the hydrodealkylation section. After conversion of the reformers to
operation on KR series catalysts, the concentration of hydrogen in the HRB is at least 80%
by volume.
Pilot-plant tests have demonstrated the feasibility of using reformer HRG in the catalytic hydrodealkylation process. Moreover, it has been found that the trace amounts of hydrogen sulfide present in the reformer HRG have a favorable effect on the stability and activity of the alumina-chromia catalyst used in the benzene production unit [i]. This effect
is explained on the basis of the theory of regulated phase transitions [2].
When using reformer HRG in the catalytic hydrodealkylation section, the benzene production unit was revamped so as to eliminate the hydrogen production section (Fig. ib). Optimal
conditions in catalytic hydrodealkylation are provided by mixing HRG taken directly from the
reformers with reformer HRG that has passed through the naphtha hydrotreating section.
In
the proposed scheme, provisions are made for supplying the excess reformer HRG in two different versions of the process.
With a hydrogen concentration above 82% by volume the HRG is supplied to the hydrodealkylation section under pressure of 1.8 MPa; with a hydroBen concentration below 82%, the HRG
is supplied under pressures of both 1.8 MPa and 5 MPa. In both versions, the HRG supplied
under a pressure of 1.8 MPa is further compressed in the compressor section to 5 MPa. In
the second version, the balance quantity of HRG with a hydrogen concentration of 65~ by volume is passed over to the diesel fuel hydrotreatin~ units.
Since part of the gas has previously passed through the naphtha hydrotreating section, it is possible to regulate the
trace quantities of hydrogen sulfide in the HRG circulating in the benzene production unit.
An analysis of the material balances before and after revamping the benzene production
unit (Table i) demonstrates that the operating costs have been reduced as a result of lower
consumption of fuel gas and chemically treated water. Comparative data on the consumption
of fuel and energy resources are presented in Table 2. By increasing the diameter of the
gas takeoff line from the top of the stabilizer column, it has become possible to obtain
benzene with the required quality (Table 3), in spite of a considerable increase in the output of stabilizer gas as aconsequence of the catalysate absorbing propane and butane from
the makeup HRG.

I. M. Gubkin 5~scow Institute of Oil and Gas.

Topliv i Masel, No. 9, pp. 17-19, September, 1987.

418

0009-3092/87/0910-0A18512.50

Translated from Khimiya i Tekhnologiya

9 1988 Plenum Publishing Corporation

TABLE i
IAcclto IAfter revamping
laeslgn
iI
o
vers. I vers.

Product

Taken, wt. %
Feed
100.00
Process steam from
35,20
reformer furnac9
Hydrogen-rich gas
-Inc
100% hydrogen
-Total

135,20
Obtained, wt. %
Commercial benzene
80,50
i,80
Stabilizer ~ases
Methane-rich gas
15,00
Including gas used within
5,40
the unit
Carbon dioxide to a~mos.
15,60
22,30
Steam c6ndensate
Exces~ h~d~bgefi-rid~
gas
Including I00~ hydrogen

_ ..Total 135,20

100,00

100,00

--

--

10,90
2,78

13,22
3,15

110,90

113,22

80,50
3,60
26,80
3,13

80,50
3.70
25,33
3,13

3.69
0,37

110,90 113,22

TABLE 2
I
Consumption
Savings
Fuel and energy resources Ace. to Iafter
design ] vampin~ Fuel ~as for conslu~ption
within unit~ kg, h
Chem. treated water for
steam generaBion, kg/h
Including process steam,
kg/h
Electrical ehergy, kW-h
Steam, k~/h

1352

589

7090

--

6593
2100
2224

763

6593

1934
--

166
2224

TABLE 3
I Benzene from unit
after
design
vamping

Index

Density at 20~ kg/m S

Crvsnaiiization temp.~ =C
Impurity cont., wt.
Distillation interval, =C

878--880
5.4 Min.
0.1 Max.
0.6 Max.

878--880
5,4--5.43
0,01--0,03
0,5--0,6

Fig. i. " Flow plan of unit: a) as designed; b) after

revamping; i, 2, 3) respective sections for hydrodeaikylanion, hydrogen production, and cryogenic treatment of h y d r o g e n - r i c h gas; I) feed; II) benzene; III,
IV, V) 65, 90, and 95% h y d r o g e n - r i c h gas, respectively;
VI) carbon dioxide; VII) chemically treated water; VIII)
m e t h a n e - r i c h gas; IX, X) makeup h y d r o g e n - r i c h gas, highpressure and low-pressure, respectively; XI) excess hydrogen-rich gas.

419

In the course of fixed runs, a favorable effect was demonstrated for optimal trace
amounts of added hydrogen sulfide in the circulating HRG. With identical length of the runs
and insignificant differences in the feed composition, the presence of trace amounts of hydrogen sulfide were found to give a sharp decrease in the rate of temperature rise in the
reactors, indicating that the stability of catalyst operation had been improved. Moreover,
the conversion of aikylaromatic hydrocarbons was increased slightly; this was indicated by
increases in the average temperature drop in the reactors and in the content of benzene in
the high-pressure separator, and also by a decrease in the quantity of recycle.
As a result of replacing high-hydrogen gaseous fuel by methane-rich gas, the operation
of a number of refinery units was improved. Because of the possibility of making the circulating HRG heavier, the operational reliability of circulating compressors in the diesel
fuel hydrotreating unit was improved.
LITERATURE CITED
i.
2.

420

V. I. Goiubyatnikov and V. M. Kapustin, in: Summaries of Papers from Conference of Young

Scientists and Specialists [in Russian], NIIneftekhim, Ufa (1985), p. 24.
R. Z. Safieva and Z. I. Syunyaev, Khim. Tekhnol. Topl. Masel, No. ii, 4-6 (1986).