RU1825653C - Catalyst for isomerization pinene into camphene and tricyclene - Google Patents

Abstract

The inventive catalyst contains 0.5-0.6 wt.%, In terms of metal, nickel sulfate, or cobalt sulfate, or ferrous sulfate BF NiSO / i, or CoSO-j, or 5.7-5.9 wt. %, in terms of sodium, sodium hydroxide BF NaOH and the rest hydrated titanium dioxide BF TJaa. NaOH and TI02 are placed in the flask. The mixture was boiled for 6 hours with stirring. After washing, formic acid is added to the mixture with washing. The catalyst is washed, filtered and dried. Catalyst characteristic: static exchange capacity 0.24-0.26 mEq / g, specific surface 135 m / g. volumetric rate of continuous isomerization of 0.4-1.1 hours 1 tab. Yo

Description

The invention relates to catalysts for the isomerization of unsaturated terpene hydrocarbons, in particular to a catalyst for the production of camphene and tricyclene.

The purpose of the invention is to increase activity while maintaining selectivity for the yield of camphene and tricycylene above 80% (4).

This goal is achieved by the fact that in the catalyst containing hydrated titanium dioxide and sodium hydroxide, nickel sulfate or cobalt sulfate, or iron sulfate is additionally introduced in the following components, May%:

Nickel sulfate or sulfate

cobalt, or iron sulfate,

in terms of metal 0.5-0.6

Sodium hydroxide, in

in terms of sodium 5.7-5.9

Hydrated

titanium dioxide

The proposed catalyst is illustrated by the following examples, and in order to clarify the effect of the additives in Example 1, the catalyst is prototyped, and the catalysts characterizing the present invention are given in the remaining examples.

Example 1. 400 ml of 25% NaOH are placed in a flask and 90 g of titanium dioxide are poured. The mixture is boiled for 6 hours while stirring. After washing and decanting the alkaline solution twice, the residual alkalinity is 2.8% NaOH. To this mixture is added with stirring.

20 ml of 85% formic acid until the acidity of the aqueous layer is 0.15%. Then the catalyst is washed until the washings are neutral, filtered off and dried at 100-105 ° C.

The resulting catalyst has the following characteristic:

Static exchange capacity 0.23 mEq / g

The sodium content of 6.2%

The specific surface is 134 mg / g. Example 2 400 ml of 25% NaOH are placed in a flask and 90 g of dry titanium dioxide are poured. Analogously to Example 1, treatment and washing are carried out to a residual alkalinity of an aqueous layer of 3% NaOH. 8, this mixture was added with stirring 22 ml of formic acid until the acidity of the aqueous layer was 0.2%. Then, 2.7 g (nickel sulfate heptahydrate) was added to the flask. The mixture was stirred for 2 hours. After this, the catalyst was treated as in Example 1. The resulting catalyst had the following characteristic: Static exchange capacity 0.24 mEq / g

Sodium content 6.0% Nickel content 0.1%

The specific surface area is 135 mg / g. Example C 3. Analogously to Example 2, a catalyst was prepared, but 7.2 g of nickel heptahydrate was added. Further processing of the catalyst is repeated in the same manner as in Examples 1 and 2.

The resulting catalyst had the following characteristic:

Static exchange capacity 0.25 mEq / g,

Sodium content 5.9% Nickel content 0.5%

The specific surface area is 135 mg / g. Example 4. Similarly, only with the addition of 8.1 g of nickel sulfate heptahydrate was a catalyst obtained which had the following characteristic: Static exchange capacity 0.26 mg eq / g,

Sodium content 5.8% Nickel content 55%, Specific surface area 135 m2 / g. Example 5. Similarly, only with the addition of 9 g of nickel sulfate heptahydrate was a catalyst obtained which had the following characteristic: Static exchange capacity 0.26 mEq / g,

Sodium content 5.8% Nickel content 0.6% Specific surface area 135 mg / g

Example 6. Similarly. Only with the addition of 13.5 g of nickel sulfate heptahydrate was a catalyst obtained that had the following characteristic:

Static exchange

capacity 0.26 mEq / g.

Sodium content 5.6%. Iron content 0.76%. Specific surface area 135 mg / g.

Catalysts with the addition of iron sulfate and cobalt sulfate were prepared in a similar manner.

The catalysts according to the invention have been tested in the process of continuous isomerization of pinene into camphene and tricycylene,

A catalyst sample is loaded into a flow-type reactor with a working volume of 10 cm3 with a thermostatic jacket and with temperature measurement in the reaction zone.

The process temperature is maintained at 130 ± 0.5 ° C. The pinene micropump is fed from below, and reaction products are introduced from above. The feed rate of pinene is regulated and set so that at the outlet of the reactor as part of the reaction product there is no slip of pinene. The variable parameter, as shown in the table, was the content of promoters in the catalyst, which determined the space velocity during the complete conversion of pinene at its slip boundary.

The results of the comparative activity of the known and proposed catalysts are shown in the table.

From the above data it can be seen that

the proposed catalyst causes an increase in the rate of pinene isomerization by three times while maintaining high selectivity for the sum of the target products.

Claims (1)

SUMMARY OF THE INVENTION A catalyst for the isomerization of pinene into camphene and tricycylene containing hydrated titanium dioxide and sodium hydroxide, characterized in that, in order to increase the activity of the catalyst, it further comprises nickel sulfate, or cobalt sulfate, or iron sulfate in the following components: wt.%: Nickel sulfate, or cobalt sulfate, or iron sulfate (in terms of metal) 0.5-0.6 Sodium hydroxide (in terms of nitride) 5.7-5.9 Hydrated titanium dioxide