P L A N T FOR CATALYTIC

AND

ISOMERIZATION

OF N - P E N T A N E

ITS P R I N C I P A L O P E R A T I N G C H A R A C T E R I S T I C S

V, A. S h e s t a k o v , N. R. B u r s i a n , V, L. K l i m e n k o , S. S. R o z e n o e r , N. K. V o l n u k h i n a , a n d I. A. V o l k o v

UDC 665.656,2

The catalytic isomerization process of n-pentane to isopentane is of great interest as isopentane is used widely in the production of isoprene rubber, as a solvent for isoprene polymerization, as a fuel component for high-compression internal combustion engines, and for other purposes. A number of multi-ton industrial n-pentane isomerization plants have been constructed and are operating currently on the basis of a process developed in the All-Union Scientific-Research Institute of Petrochemical Processes under the Giprokauchuk project. The catalyst used in the process is IP-62, which is distinguished by high activity, selectivity, and stability. If necessary, it can be oxidation-regenerated. In this paper we shall consider the resutts of operating a plant for the isomerization of n-pentane over the first year of operation. The raw material used in the plant is the pentane fraction separated from gasoline in the Petroleum Stabilization Plant, Gasoline Plant, and Petroleum Processing Plant refluxes of the Central Installation for Gas Fractionation (CIGF). The hydrocarbon composition of the raw material, its sutfur and moisture content are shown in Table 1. In the isomerization process, hydrogenous gas is used (density 0,36 g/liter) from a catalytic reforming plant, which has an average chemical composition (vol.%) as follows: H. . . . N;
O~ . . 9

79.5 0s
0.2

Ca . . , c, ...
C~ . . .

CI . . . C2 . . 9

4,7
6.9

C6 . , .

4.7 2:2 0.5 0,5

Figure ! shows the technical block diagram of the plant. The n-pentane fraction from the CIGF enters storage and then passes to column 11 for removal of the heavy components. If necessary, this same column can handle the recycled n-pentane fraction. The heavy components of the raw material are drawn off from the vat of column 11, the head product of which is n-pentane, and then pass on to the azeotropic drying column 12. The mixture of dried n-pentane and recycled n-pentane is admitted for isomerization and, together with the circulating hydrogen gas,it is heated up to 300*(: in the heat exchanger 21 (due to the heat of the reacting gases) and to 500"C in the tubular furnace 23. The isomerizafion reaction takes place in the reactor 24, filled with catalyst, at a temperature of 380-450"C and an excess pressure of 35-40 atm. The heat of the reacting gases is utilized in the heat exchangers 21 and 22. The reaction gases are cooled to 40"C and condensed by the condenser 17. The gas is separated from the liquid reaction products in two stages: at a pressure of 30 atm in the separator 18 and at 10-14 arm in the separator 20. The low-pressure gas separated is discarded into the fuel tine. The gas from separator 18 (circulating hydrogen) is fed to the compressor 2 for drying by molecular sieves in the adsorber 36, together with fresh hydrogen supplied by the compressor 1. All-Union Scientific-Research Institute of Petrochemical Processes. logiya Topliv i Masel, No. 11, pp. 14-17, November, 1971. Translated from Khimiya i Tekhno-

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TABLE

i. Characteristics of Isomerization Raw Material

Content, wt.% of Raw material
iso -

pentane Pentane fraction on exit to works: according to MRTU 38-1-212-66 actual .............. Pentane fraction recycle: planned . . . . . . . . . . . . . . . . actual . . . . . . . . . . . . . . . . Pentane fraction on isomerization: planned . . . . . . . . . . . . . . . . actual . . . . . . . . . . . . . . . . no more than 5,0 5.0 no more than 3.1 5.0 no more than i.9 6.65

n-pentane

Cs and above

sulfur

moisture no more than 0.009 0.011

no more no less than 88.0 no more than 5.0 than 0.01 88.7 5.3 0.01-0.02 no less than 96.2 no more than 0.7 4.5 90.5 no less than 97.5 no more than 0.6 90.8 2.2

0.00016

0.006

0.008 no m ore than 0.002 0.007

TABLE 2. Composition of Rectified Isopentane (wt.%) Components Isopentane . . . . . . . . . . . . . n-Pentane . . . . . . . . . . . . Total hydrocarbons CI-C 4 . . Hydrocarbons C6 and higher . Fluorine compounds . . . . . . Sulfur .............. Cyclopentadiene . . . . . . . . Planned not less than 96.7 not more than 2.0 not more than 0.8 not more than 0.5 absent not more than 0.005 not more than 0.0003 Actual

98.57 1.05 0.34 absent 0.00000149 43.00035 0.00011

"

26
9

'27
~o

37
2

1"11

Fig. 1. Technical block diagram of plant: 1, 2) hydrogen compressors; 3-10)pumps; 11,14, 15)rectification; columns; 12) azeotropic drying columns for raw material; 13) steaming columns; 16) receiver; 17) condenser; 18) separator; 19) high-pressure receiver; 20) lOwkpressure receiver; 21, 22) hydrocarbon and hydrogen heat exchangers; 23) furnace; 24) reactor; 25) precontactors; 26-29) fractionating columns; 30-33) receivers;34-37) adsorbers; 38, 39) refrigerators; 40) florentine receptacle. Flows: I) n - p e n t a n e fraction; II) n - p e n t a n e fraction recyc!e; IID Cs (to storage); IV) KhZK; V) CI-C4; VI)iso-Cs; VII) fresh hydrogen.

820

Reactor temperature, ~
3g0,-

50

4 ~Z Ca

^ Cs and higher

~ m

.-

l
I

Moisture in raw material, wt. %

I I I I I I

,9

II

15

15

,g

II

/3

15

Time, ;month~. Fig, 2. Characteristics of the isomerization process on an aluminum-platinum catalyst,

Time, months Fig. 3. Moisture content of raw material entering the reactor and in the circulating hydrogenous gas (after drying).

The liquid reaction products are separated in two columns 14 and 15 working in series, into C 4 hydrocarbons, isopentane and pentane fractions. The adsorber 34 is intended to trap traces of fluorine from the isopentane; aluminum 7-oxide is used as the adsorbent. Reactor Unit. The isomerization process is carried out in the vapor phase in a reactor under pressure and with circulating hydrogenous gas. The reactor is a hollow vessel with a thermally insulated lining shielded by a stainless steel casing and which is filled with catalyst. An a l u m i n u m - p l a t i n u m catalyst IP-62 on aluminum 7-oxide activated by fluorine is used as the catalyst. The catalyst, freshiy charged into the reactor, is subjected in succession to firing for the purpose of removing moisture and then to reduction in a hydrogen medium. The isomerization reaction takes place on the catalyst, together with n-pentane and isopentane cracking. Simultaneously, hydroscrubbing of the n-pentane and isopentane takes place. The specific weight of these reactions is controlled by the composition of the catalyst and by the process conditions. It was established in [1] that the isomerization reaction must proceed to a finite depth which, for IP-62 catalyst, is limited by the magnitude of n-pentane conversion after one operation, equal to 50-55% by weight. In this case the yield of breakdown products does not exceed 2% by weight. The high selectivity of the isomerization process depends upon the low thermal effect of the process which excludes the necessity for intermediate cooling. Simultaneously with the isomerization process, desulfurization reactions take place on the IP-62 catalyst of n-pentane and isopentane with the formation of hydrogen sulfide [2]; the latter is removed when blowing off the circulating gas and when stabilizing the catalyzate. A study of the kinetics of the process showed that the isomerizatton reaction velocity of n-pentane is directly proportional to the partial pressure of hydrogen. Change of the operating pressure within the limits of 15-100 atm has no significant effect on the reaction velocity [3]. On the basis of the runs carried out, a working pressure of 35-40 atm, n-pentane partial pressure of 5-10 atm, and a molar ratio of hydrogen to sulfur equal to 3 : 1 were chosen. A study of the effect of the bulk velocity of admission of n-pentane at a temperature of 860-450"C, a pressure of 40 atm, and a molar ratio of hydrogen to pentane equal to 2.9 : 1 permitted us to determine the temperature limits for conducting the process at 360-450"C with a bulk rate of raw material feed of l h , 1 [1]. The run was started at a temperature of 365"C, and over a long time of operation of the catalyst the t e m perature in the reactor did not exceed 385"C. The pressure in the reactor was maintained at 36 arm. Thus, the catalyst has a reserve of activity with respect to temperature and selectivity (Fig. 2).

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The lifetime of the catalyst was planned as 6 months with regeneration to be carried out after 3 months. In fact, the tP-62 catalyst functioned without intermediate regeneration for 15 months and maintained an adequately high activity and selectivity (see Fig. 2). The quality of the catalyst in all characteristics is of the same level as that of foreign catalysts used in the high-temperature isomerization process of paraffin hydrocarbons. Plant for Preparation of Raw Material, Separation of Finished Product, and Stabilization of Catalyzate. The unit consists of three rectification columns 11, 14, and i s and an azeotropic column 12 for drying the raw material. The rectification columus are designed for the separation of isopentane and hydrocarbons boiling over above n-pentane from the fresh and recycled pentane fractions. A limitation in isopentane content in the n-pentane fraction achieved by isomerization (see Table 1) is caused by the reversibility of the isomerization reaction and by the tendency to reach maximum utilization of the reaction volume as the intensity of isomerization decreases proportionally with the isopentane content in the initial raw material. By these same considerations and also with the necessity for protecting the catalyst from coking, the content of C6 hydrocarbons is restricted. The sulfur content of the pentane fraction must be not more than 0.01% by weight; a specific content of sulfur in excess of 0.01% by weight leads to poisoning of the catalyst [4]. The necessity for thorough drying of the raw material is dictated by the fact that the velocity of the n-pentane isomerization reaction decreases with increase of the amount of moisture in the raw material [5]. The raw material, on entry to the plant (from the CIGF) satisfies the requirements of the project except for the content of sulfur compounds, which amounts to 0.01-0.02% by weight. The pentane fraction fed to the reactor for isomerization does not correspond to the requirements of the process (see Table 1) in respect to the content of isopentane, n-pentane, C~ hydrocarbons, and moisture, This is explained by the unsatisfactory operation of columns t l and 12. The rectified isopentane with respect to hydrocarbon composition and impurity content meets the requirements for the isopentane used as raw material for the production of isoprene and can be used as the solvent in the polymerization of isoprene (Table 2). By-products of the process are hydrogeneons gas of composition Ci-C 4 t o 1-2% by weight on the raw material (per run). Stabilization of the catalyst is effected in column 14, which serves to remove light hydrocarbons. In view of the insignificant quantities of gaseous products, the latter enters into the fuel supply of the factory. Purification . of Hydrogenous Gas and Drying of Circulatin~ Gas. According to specification the hydrogenous gas should be subjected to purification by the IP-62 catalyst from CO, CO s, O2, and unsaturated hydrocarbons. Because reforming gas is used, in which the impurities mentioned are absent, there was no necessity for this stage and, consequently, units 25 and 36 are left out of the diagram. Fresh hydrogenous gas is fed into the circulating gas line. The mixture of fresh hydrogen and circulating gas undergoes drying in type NaA zeolites (in the adsorbet 36), is mixed with n-pentane, and then enters the isomerization reactor. The negative effect of moisture on the activity and selectivity of the catalyst, and also the possibility of increasing the rate of removal of fluorine from the catalyst, is taken into account; two methods are provided for protecting the catalyst from the action of moisture: a) azeotropic drying of the raw material in column 12; b) ~ y i n g the circulating hydrogenous gas by molecular sieves in the adsorbers 36. The drying agents in 36 function alternately. The circulating hydrogenous gas for drying passes through one of the driers and, simultaneously, in the second drier regeneration of the zeotites takes place. During the run the molecular sieves were subjected to repeated regeneration (60 cycles), thus maintaining mechanical rigidity and sufficient dynamic activity to moisture. The moisture content in the circulating gas after drying the gas on zeolites throughout the entire run did not exceed the regulation requirements (see Fig. 3). Moisture control of the gases was effected by means of a coulombometric continuously operating, automatic recording instrument of type KIVGI (Irkutsk Branch of the Siberian Academy of Sciences). Chromatographs are installed in the flow for continuous monitoring of the hydrocarbon composition.

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The low consumption of hydrogen in comparison with the planned consumption is explained by the periodic discharge of gas from the n-pentane isomerization plant, in contrast with the constant discharg e specified in the plan, and also the actual hydrogen consumption by the isomerization reaction and dissolution of the isomerizate obviously was lower than planned. It should be noted that the periodic discharge of hydrogen from the system is possible only when an increase in the hydrogen sulfide concentration does not lead to a reduction of activity and selectivity of the catalyst. As a result of checks carried out on the n-pentane isomerization process in an industrial plant, it was established that: a) the duration of the nonregeneratiVe raw-material cycle amounts to 16 months instead of the 3 months specified in the plan; b) the IP-62 catalyst has an activity which permits the volume rate of feed of raw material to be increased from 1.0 to 1.5 h -l (with a 1-year lifetime of the catalyst); c) the consumption of hydrogen can be reduced by a factor of 2, due to the use of periodic discharge of hydrogenous gas instead of continuous discharge assumed in the plan; d) the molecular NaA sieves, used for drying the circulating gas during the 15 months, provided the necessary moisture content and had good regenerative capability. Thus, the planned characteristics were achieved and exceeded, the excellent operating qualities of the IP-62 catalyst were proved, and the correctness of the technology developed for the process and the satisfactory and reiiable operation of the plant were also proved.
LITERATURE CITED

i. 2. 3. 4. 5.

N.R. Bursian, N. K. Volnukhina, and G. N. Maslyanskii, Khim. Prom., No, 3 (1961). N.R. Bursian, N. K. Volnukhina, G. N. Maslyanskii, and S. S. Rozenoer, Author's Certificate 234999, Byull. !zobret., No. 5 (1969). N.R. Bursian and N. K. Volnukhina, Zh. Prikl. Khim, 38, 2273 (1965). N.R. Bursian and N. K. Volnukhina, Zh. Prikl. Khim, 3--9, 656 (1966). N.R. Bursian and N. K. Volnukhina, Zh. Prkl. Khim., 39, 845 (1966).

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