SU1182019A1 - Method of producing tetralin - Google Patents

Description

The invention relates to methods for producing tetralin from naphthalene, and can be used in the refining and petrochemical industries. five

The purpose of the invention is to increase the yield of the target product and the selectivity of hydrogenation. '

Example 1. A naphthalene solution containing a naphthalene in a hydrocarbon-10 diluent with a sulfur content in terms of naphthalene of 0.24 wt.%,

The hydrogenation feedstock is a 20% solution of naphthalene in a diluent hydrocarbon (toluene ^, yes · sulfur content in, 5 terms of 1 hectare naphthalene 0.0005 wt.%.

5 cm ³ of the zirconium-nickel alloy hydride is placed in the reactor and a sulfuring agent is fed at 220 ° C for

4 hours at a volumetric rate of 1.0 h " ¹ , resulting in the catalyst being sulfurized. Next, the hydrogenation feedstock is mixed in a mixer with hydrogen and fed to a reactor heated to 220 ^° C, where the sulfurized kata-25 is located. Hydrogen feed rate

2.5 l / h, feed rate

5 ml / h. The pressure is atmospheric. The yield of tetralin 80%. Selectivity of 80%.

Example 2. The carbonizing agent and the hydrogenation feedstock are similar to those described in Example 1.

5 cm ^{3 of the} hydride of the zirconium alloy with nickel is placed in the reactor and the sulphurization agent is fed at 240 ° C for 6 hours with a volume rate of 1.0 h ¹ , as a result of which the catalyst becomes grayish. Next, the hydrogenation feedstock is mixed in a mixer with hydrogen and fed into the reactor, heated to 220 ° C, where the sulfurized catalyst is located. Hydrogen feed rate

2.5 l / h, feed rate 5 ml / h. The pressure is atmospheric. The yield of tetralin 84,4%. Selectivity of 85%.

Example 3. The carbonizing agent and the hydrogenation feedstock are similar to those described in Example 1.

ί 5 cm ³ of zirconium-nickel alloy hydride is placed in the reactor and 50 sulfurizing agent is fed at 220 ° C for 8 hours with a volume rate of 1.0 h ' ¹ , resulting in catalyst grayening. Next, the hydrogenation feedstock is mixed in a mixer with hydrogen and fed to a reactor heated to 220 ° C, where the sulphurized catalyst is located. The feed rate of hydrogen is 2.5 l / h, the feed rate of raw materials is 5 ml / h. Atmospheric pressure. Tetralin yield 98.5%. Selectivity is close to. 100%.

Example 4. The carbonizing agent and the hydrogenation feedstock are similar to those described in Example 1.

5 cm ^{3 of the} hydride of the zirconium alloy with nickel is placed in the reactor. The sulfurizing agent is fed at 23Ο ^σ Ο for 10 h with a bulk velocity of 1.0 h ^-1 , as a result of which the catalyst becomes sulphate. Next, the hydrogenation feedstock is mixed in a mixer with hydrogen and fed into the reactor, heated to 220 ° C, where the sulfurized catalyst is located. Hydrogen feed rate

2.5 l / h, feed rate 5 ml / h. The pressure is atmospheric. The yield of tetralin is 99.8%. The selectivity is 100%.

Example 5. The carbonizing agent and the hydrogenation feedstock are similar to those described in Example 1.

5 cm ³ of zirconium-nickel alloy hydride is placed in the reactor and a sulfuring agent is fed at 22 ° C. for 12 h with a volumetric rate of 1.0 h ~ ^l , as a result of which sulphurization of the catalyst occurs. Next, the hydrogenation feedstock is mixed in a mixer with hydrogen and fed into the reactor, heated to 220 ° C, where the sulfurized catalyst is located. Hydrogen feed rate

2.5 l / h, feed rate 5 ml / h. The pressure is atmospheric. The yield of tetralin is 90%. Selectivity? 100%.

Example 6. The carbonizing agent and the hydrogenation feed are similar to those described in example 1.

5 cm of the zirconium – nickel alloy hydride is placed in the reactor at 220 ° C for 20 hours at a space velocity! h, as a result, the sulphurization of catalysates occurs.

Next, the hydrogenation feedstock is mixed in a mixer with hydrogen and fed into the reactor, heated to 220 ° C, where the sulfurized catalyst is located. The feed rate of hydrogen is 2.5 l / h, the feed rate is 5 ml / h. The pressure is atmospheric. The yield of tetralin 57,7. Selectivity is 100%.

The results of these experiments are summarized in Table 1, which shows the dependence of the activity of the catalyst of zirconium hydride alloy with nickel in the hydrogenation of naphthalene in tetralin at 220 ° C ^with duration of sulfurization.

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Table 1

The duration of sulphurization, h

The composition of catalyzate, wt.% (Excluding hydrocarbon diluent)

. 1EalElin [Decalin _ ^ _ Naphthalene Selectivity

four 80 20 - 80 6 84.4 15.4 0.2 85 eight 98.5 1.5 - 100 ten 99.8 Traces - 100 12 90 ten one 100 20 $ 7.7 - 42.3 100

As can be seen from Table 1, with an increase of 20 times the duration of serification from

4 Up to 10 h, the yield of tetralin and the selectivity of the hydrogenation process increase, and the yield of decalin is reduced to a practical absence of 25 when the carbonation time is 10 h. A further increase in the duration of sulphidation leads to a decrease in the yield of tetralin, with a constant selectivity of the process of hydrogenation of zonaphthalene to tetralin. The catalyst has maximum activity.

and selectivity in the event that the blackening is carried out for 8-10 hours

In this case, there is a practical absence of by-products of scale, which indicates a high selectivity,

Effect of sulfur content of the agent in tetralin osernyayuschem yield given in Table 2 (thionation conditions: temperature 230 ° C, duration 10 hours thionation hydrogenation conditions for all the experiments: temperature 220 ^s C H ₂ flow rate of 2.5 l / h flow rate raw materials - 45

5 ml / h, atmospheric pressure).

table 2

Sulfur content sulking agent wt.% The yield of tetralin, wt.X Selectivity, X one ______one.______ 3

0.1 34.2 40

0.18 60.0

65

Continuation tabl one 2 3 0.24 99.8 100 0.4 70,8 100 0.5 41.5 100

As can be seen from the data given in Table 2, the maximum yield of tetralin is achieved when the sulfur content in the soodilating agent is 0.24 wt.X, and the optimum ratio is 0.18-0.4 wt.X of sulfur in the sulfurizing agent.

The effect of temperature of sulphurization on the yield of tetralin is given in Table 3. (conditions of sulphurization: the duration of sulphurization is 10 h, the volumetric rate is 1.0 h ' ¹ ).

Table 3

Temperature Tetra output Selective Aging, ° C lina, wt.% ness, X

180 60 60 200 72.5 80 220 98.5 100. 230 99.8 100 240 99.0 ' 100 260 89.5 95 280 64.5 60

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From the data of Table 3 it can be seen that the maximum yield of tetralin is observed when the catalyst is sulphurized in the temperature range 220-240 ° C.

The influence of the catalyst sulphate volume rate on the tetralin yield is given in Table 4 (sulphurization conditions: sulphurization duration 10 h, sulphurization temperature 230 ° C).

Table 4

Bulk speed of sulphurization, h ~ ¹ d — Tetralin yield, May Selectivity,% 0.2 45.5 50 0.5 61.5 65 1.0 99.8 100 1.5 57.2 100 oh oh 35 ' 100 5.0 18.0 100

As can be seen from the data presented in Table 4, the maximum yield of tetralin is achieved when the catalyst becomes sulphurised with a bulk velocity of 0.51.5 h " ¹ .

The effect of hydrogenation temperature on the yield of tetralin is given in table 5

Table 5

Temperature with The yield of tetralin, wt.% Selectivity,% , 180 80.4 100 200 ’ 89.5 100 220 99.8 100 , 240 96,8 98 260 82.5 90

From the data of Table 5 it can be seen that the maximum tetralin yield is achieved in the temperature range 200-240 ° C.

The duration of the catalyst without regeneration is not less than 1000 hours

Claims (2)

1. METHOD OF OBTAINING TETRALINE by vapor-phase hydrogenation of naphthalene in the presence of a diluent at elevated temperature and atmospheric pressure in a hydrogen environment on the catalyst of the zirconium-nickel alloy hydride, characterized in that, in order to increase the yield of the target product and the selectivity of the process, the catalyst is pre-grayed with naphthalene containing 0.18-0.4 wt.% sulfur, at 220-240 ° C, space velocity 0.5-1.5 h ' ¹ for 8-10 hours 2. Method pop.1, characterized in that the hydrogenation is carried out at 200-240 ° C. with € ω with 1 182019 2