SU407436A1 - - Google Patents

Description

CATALYST FOR CONVERSION OF HYDROCARBONS

12

The invention relates to the production of catalysts for the conversion of hydrocarbons, for example isomerization, alkylation, cracking.

A known catalyst for the conversion of hydrocarbons containing the nlatinic metal of the supported group is alumina.

The disadvantage of this catalyst is its insufficiently high activity and selectivity of action.

In order to eliminate these drawbacks, a catalyst is proposed for the conversion of hydrocarbons, for example isomerization, alkylation, cracks 1 ga, including a carrier, preferably alumina, a metal of the nlatian group in an amount of from 0.01 to 2 wt. %, nickel - from 0.01 to 5 weight. %, metal IVA group of the periodic table, preferably germanium or tin - from 0.01 to 5 weight. % In addition, the catalyst may contain chlorine or a compound of chlorine in the amount of more than 1.5 weight. % in terms of chlorine and sulfur or sulfur compound in an amount of not more than 0.5 weight. % in terms of sulfur.

As a platinum group metal, it is desirable to use platinum. The atomic ratio in the nickel to platinum metal catalyst is between 0.2: 1 and 20; 1 and the atomic ratio of a metal of group IVA to

the platinum group metal is from 0.5: 1 to 10: 1.

Example 1. Alumina carrier material consisting of 1.6 mm balls was prepared as follows. Aluminum hydroxyl chloride sol, a solution of pure aluminum granules in a solution of hydrochloric acid were obtained by adding hexamethylene tetramine to the resulting sol, and the resulting solution was gelatinized by dropping it in an oil bath to obtain spherical particles of an aluminum hydrogel. The resulting particles were subjected to aging and washing and, finally, dried and burned aged and washed particles to form spherical particles of gamma-alumina containing approximately 0.3 weight. % added chloride.

Measured amount of tetrachloride

0 germanium compounds were dissolved in anhydrous ethanol. The solution was kept at room temperature until equilibrium was reached. Then prepared an aqueous solution containing chloroplatinum acid,

5 nickel chloride and hydrogen chloride. Thereafter, the two solutions were well mixed and used to impregnate the gamma-alumina particles in amounts appropriately calculated to obtain the final mixture.

0 containing germanium 0.5, nickel 0.5 and 0.375

weight. % platinum. In order to ensure a uniform distribution of the metal components throughout the carrier material, this impregnation step was carried out by adding particles of the carrier material to the impregnated mixture with constant stirring, in addition, the solution volume was approximately twice the carrier material volume. The impregnation mixture was maintained in contact with the particles of the material for about 0.5 hour at 21 ° C. After that, the temperature of the impregnation mixture was increased to approximately 107 ° C, and the excess solution was evaporated for approximately 1 hour. Then, the obtained dried particles were subjected to firing in air at a temperature of approximately 496 C for 1 hour. After that, the burnt balls were in contact with the air stream, containing H20 and HC1 in a molar ratio of about 40: 1, for about 4 hours at 524 ° C in order to bring the halogen content in the catalyst particles to about 0, 9 wt. %

The obtained catalyst particles were analyzed and it was found that they contain (approximately) platinum 0.375, germanium 0.5, nickel 0.5 and chloride 0.85 weight. % The atomic ratio of nickel to platinum was approximately 4.4: 1; The atomic ratio of germanium to platinum was 3.56: 1. After that, the catalyst particles were subjected to a dry reduction treatment for 1 hour by contacting a gas containing hydrogen at a temperature of approximately 583 ° C, a pressure slightly above atmospheric. 11 catalyst particles corresponding to the gas hourly space velocity or volume velocity per hour at 15 ° C.

Example 2. In order to compare the proposed catalytic mixture with the platinum-germanium mixture, an experiment was carried out. The catalyst was prepared as in example 1, with the exception of nickel, which resulted in a reforming catalyst comprising platinum 0.375, germanium 0.5, chloride 0.85 weight. % with alumina carrier material.

Then, the relative activity of the selectivity in the process of reforming the gasoline mixture of these tri-n bimetallic catalysts was tested separately. In all experiments, the same feed mixture was used, its characteristic is given. The test was carried out essentially with the absence of sulfur and water, the only source of sulfur was 0.5 parts of sulfur per 1 million in the charge, and the only significant source of water was 5.9 weight. hours of water for 1 million in loading.

Analysis of heavy Kuwaiti oil Specific gravity (15.6 ° C) 0.7374

Initial boiling point, ° С85

Boiling point of 10% fractions, ° С 96

Boiling point of 50% of fractions, ° С124

Boiling point of 90% fractions, ° С161

Final boiling point, ° С182

5 Sulfur weight. hours at 1 ppm

Nitrogen, per 1 million OD

Aromatic hydrocarbons,% by volume 8 Paraffins, vol. % 71

Naphthenes, about. % 21

0 Water, hours for 1 million. 5,9

Octane number40

Experiments were specifically conducted to determine in a very short time whether the catalyst has superior performance.

5 for the reforming process. The experiment consisted of six periods (a six-hour period), followed by a ten-hour experiment carried out at a constant temperature, and a reformat was collected during this neorod

0 C5 +. The experiment was carried out in a laboratory reforming unit comprising a reactor containing a catalyst, a hydrogen separation zone, a butano-distillation column, appropriate heating, pumping, condensate means, and other equipment.

The hydrogen recycle stream and the feed mixture were mixed and heated, and then passed downstream through a reactor containing the catalyst as a fixed bed. The effluent was discharged from part of the reactor, cooled to approximately 13 ° C and passed to the separation zone in which the gaseous mixture enriched in hydrogen

5 separated from the liquid phase. Part of the gaseous phase was passed through a scrubber with a large outer surface, and the resulting stream of hydrogen, which was essentially free of water and sulfur, was recycled to the reactor.

0 Excess compared to what is needed to maintain the pressure in the installation, was recovered as excess separation gas. The liquid phase from the separation zone was withdrawn and passed to the butanotonic

A column in which the light fractions were retracted upward, and the flow of the reformate C5 + was separated in the form of this fraction.

In them, the following conditions were applied: 0 constant temperature, approximately 521 ° C, during the first three periods, followed by a constant temperature of approximately 538 ° C during the last three periods, hourly gas velocity 3,0, 5 pressure per the reactor outlet is 7.8 atm and the molar ratio of hydrogen to hydrocarbon at the reactor inlet is 5: 1. This two temperature test is designed to quickly and efficiently obtain two points on the resulting octane curve for a particular catalyst. Applicable conditions are selected on the basis of experience in order to obtain the maximum amount of data but the ability of the subject.

catalyst to react to a very tough operation.

The table shows separately for the proposed and reference catalysts for the test period the temperature at the outlet of the reactor, the net excess of separating gas, the yield of debutanized overhead gas to the ratio of the latter to the sum of separating gas and debutted gas and the pure octane number.

Temperatures are given in the Celsius scale, and gas outputs are given in the form of gas volumes at, 1 atm per volume of the liquid feed mixture at 15 ° C.

From the results shown in the table, it can be seen that the effect of the nickel component on the catalyst consists essentially in promoting the ilatin-erium catalyst. The proposed catalyst dramatically exceeds the control one both in activity and in selectivity.

G1 REMEDIATED AND I. A Catalyst for Constructed Hydrocarbon Accelerated Reforming Tests

Dos, for example, isomerization, alkylation, cracking, including a carrier, preferably alumina, and a platinum metal, group 5, characterized in that, in order to increase the activity and selectivity of the catalyst, it contains from 0.01 to 2 wt. % platinum group metal, from 0.01 to 5 weight. % cell, from 0.01 to 5 weight. % of metal IVA of group 0 of the periodic table, preferably germanium or o.lov.

2. Catalyst for and. I, characterized in that it contains chlorine or a compound of chlorine and an amount of not more than 1.5 wt. % in terms of la

5 chlorine and sulfur or sulfur compound in the amount of ne more than 0.5 weight. % in terms of sulfur.

3. Catalyst according to claim 1, characterized in that it contains platinum as a platinum group metal.

0 4. The catalyst according to claim 1, wherein the atomic ratio of nickel to the metal of the platinum soil is from 0.2: 1 to 20: 1 and the atomic ratio of the metal of group IV / to the metal of the ilatian group is from 0, 5: I 1.

1p11ms1allic catalysis jur (from 0, .57 ° c., | P1x.1n)

bimetallic kata.; | п la yur (nc: i nickel)