Gasoline fraction reforming catalyst and a method for preparation thereof

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

 

The invention relates to catalytic chemistry, in particular to the preparation of catalysts for reforming of gasoline fractions, and can be used in the oil industry.

The aim of the invention is to obtain a catalyst with increased activity due to the use as a carrier of aluminum oxide, where the content of oxides of sodium, iron and titanium limited, and by way of preparation, including impregnation of the alumina joint solution of hexachloroplatinic acid, ammonium perrhenate, acetic and hydrochloric acids, followed by drying and annealing with simultaneous recovery of part of the platinum.

The prior art is as follows: a known catalyst for reforming of gasoline fractions (U.S. Pat. U.S. No. 4299689, With 10 G 35/09, 1981), containing the active components on the carrier is aluminum oxide.

The disadvantage of this catalyst is its low stability. This is due to the method of its preparation and a high content of iron in the media.

Closest to the invention is a catalyst for reforming of gasoline fractions containing platinum, rhenium and chlorine on the oxide carrier, which is the composition of the oxides of aluminum, titanium and manganese (EN 2145518 C1, 17.12.98.).

The disadvantage of this aluminium oxide-platinum catalyst, p is matirovannogo rhenium, is too high in sodium and iron, inevitably remaining in the aluminum oxide at getting it through sodium aluminate, as well as a high content of additional promoters, significantly higher than the mass concentration of active components, which are inevitable in the process of long-term use leads to loss of dispersion of platinum and the impossibility of bringing it to the required level.

The INVENTION consists in the following: the invention is directed to solving the problem of obtaining a highly active catalyst for reforming of gasoline fractions.

The technical result allows us to solve the problem.

1. The technical result is achieved by using the catalyst for reforming of gasoline fractions containing platinum and rhenium oxide on the carrier, which is aluminum oxide, where the content of oxides of sodium, iron and titanium limited: Na2O - not more than 5 ppm; Fe2O3- not more than 20 ppm; TiO2not more than 2000 ppm, as platinum is part of the catalyst is restored in the metallic state in the form of platinum dichloride in a molar ratio of platinum restored in the metallic state and platinum dichloride - Pt:PtCl2=9:1-1:1 in the following ratio, wt.%: platinum (Pt) - 0,13-0,29; platinum dichloride (PtCl2) - 0,18-0,04; re is s (Re) - 0,26-0,56; media (Al2About3) - 99,43-99,11.

2. The technical result is achieved by the method of preparation of the catalyst, characterized in that the alumina is impregnated with a joint solution of hexachloroplatinic acid, ammonium perrhenate, acetic and hydrochloric acids, followed by drying and annealing with simultaneous recovery of 50-90% of platinum in the temperature range 160-550°With the rise of temperature from 160 to 280°C for 30-60 min, by creating under these conditions, the annealing reducing atmosphere due to the rapid decomposition of ammonium acetate formed during the preparation of joint impregnating solution.

The ESSENTIAL features of the invention are a composition of the carrier, the catalyst composition, the ratio of platinum restored in the metallic state and platinum dichloride, and also the method of preparation of the catalyst.

DISTINCTIVE features of the present invention is a catalyst composition, wt.%:

Platinum (Pt) 0,13-0,29;

Dichloride, platinum (PtCl2) of 0.18 to 0.04);

Rhenium (Re) 0,26-0,56;

Aluminum oxide (Al2About3) 99,43-99,11;

The sodium oxide (Na2O) not more than 5 ppm;

Iron oxide (Fe2O3) not more than 20 ppm;

The titanium oxide (TiO2) not more than 2000 ppm.

The NOVELTY of the invention consists in using as the e of the carrier of aluminum oxide, where the content of oxides of sodium, iron and titanium limited (Na2O - not more than 5 ppm; Fe2About3- not more than 20 ppm; Tio2not more than 2000 ppm); the content of platinum in the recovered metallic state and in the form dichloride in a molar ratio of Pt:PtCl2=9:1-1:1 in the following ratio, wt.%: platinum (PT) 0,13-0,29, platinum dichloride (PtCl2) of 0.18 to 0.04), rhenium (Re) 0,26-0,56, media (Al2O3) 99,43-99,11, as well as in the preparation method of the catalyst by impregnation of alumina joint solution of hexachloroplatinic acid, ammonium perrhenate, acetic and hydrochloric acids, with subsequent drying and calcination with simultaneous recovery of 50-90% of platinum in the temperature range 160-550°With the rise of temperature from 160 to 280°C for 30-60 min, by creating under these conditions, the annealing reducing atmosphere due to the rapid decomposition of ammonium acetate formed during the preparation of joint impregnating solution.

Obtaining aluminium oxide-platinum catalyst promoted with rhenium in the form in which 50-90% of platinum are in restored condition, allow us to maintain high initial dispersion of platinum on the catalyst, obtained in the described manner, in the process of transportation, storage, loading, and activation in the reforming reactors, is also in the start-up of the catalyst. This allows already in the initial period of operation to obtain a reformate with a high octane number and to maintain a high activity level during the entire period of operation.

The invention is illustrated by the following examples.

Example 1. 99,43 g of calcined oxide media, where the content of Na2O - not more than 5 ppm; Fe2About3- not more than 20 ppm; Tio2not more than 2000 ppm, vacuum for 40 min, and then placed in 200 ml joint impregnating solution containing 0,5462 g of hexachloroplatinic acid, 0,3746 g of ammonium perrhenate, 1,084 g 100% concentrated acetic acid and 3.33 g of concentrated hydrochloric acid with a concentration of 36% Hcl. The ratio of the components in the solution is:

H2Ptl6:NH4ReO4:CH3COOH:Hcl=17,1:11,7:33,7:37,5

Impregnation of the carrier is carried out at room temperature for 1 h, and then at a temperature of 80°C for 3 h with constant stirring. The excess impregnating solution is separated by decantation.

The catalyst was dried for 2 h at 60°C, 2 h at 80°C, 2 h at 120°C, 2 h at 140°C, 2 h at 160°C.

The catalyst was calcined in a stream of air with simultaneous recovery of 50% of platinum in the temperature range 160-550°With the rise of temperature of calcination from 160 to 280°C for 60 min with further increase of temperature up to 550° With speeds of 50°With an hour and aged at 550°C for 3 hours

The composition of the obtained catalyst, wt.%: platinum Pt - 0,13; platinum dichloride PtCl2- 0,18; rhenium Re - 0,26; media - 99,43.

The molar ratio of PtPtCl2:1:1.

Example 2. 99,27 g of calcined oxide carrier, similar in composition to example 1, vacuum for 40 min, and then placed in 200 ml joint impregnating solution containing 0,6092 g of hexachloroplatinic acid, 0,5908 g of ammonium perrhenate, 1,132 g 100% concentrated acetic acid and 3.33 g of concentrated hydrochloric acid with a concentration of 36% Hcl. The ratio of the components in the solution is:

H2Ptl6:NH4ReO4:CH3COOH:Hcl=17,1:16,7:32,0:34,0

The impregnation of the support and drying of the catalyst is carried out analogously to example 1. The catalyst was calcined in a stream of air with simultaneous recovery of 70% of platinum in the temperature range 160-550°With the rise of temperature of calcination from 160 to 280°C for 45 min with further increase of temperature up to 550°50°With an hour and aged at 550°C for 3 hours

The composition of the obtained catalyst, wt.%: platinum Pt - 0,21; platinum dichloride PtCl2- 0,11; rhenium Re - 0,41; media - 99,27.

The molar ratio of Pt:PtCl2=2.5 to 1.

Example 3. 99,11 g of calcined oxide carrier, similar in composition to example 1,vacuum for 40 min, and then placed in a 200 ml joint impregnating solution containing 0,6723 g of hexachloroplatinic acid, 0,8069 g of ammonium perrhenate, 1.18 g of 100% concentrated acetic acid and 3.33 g of concentrated hydrochloric acid with a concentration of 36% Hcl. The ratio of the components in the solution is:

H2Ptl6:NH4ReO4:CH3COOH:Hcl=17,4:20,9:30,6:31,1.

The impregnation of the support and drying of the catalyst is carried out analogously to example 1. The catalyst was calcined in a stream of air with simultaneous recovery of 90% platinum in the temperature range 160-550°With the rise of temperature of calcination from 160 to 280°C for 30 min with further increase of temperature up to 550°50°With an hour and aged at 550°C for 3 hours

The composition of the obtained catalyst, wt.%: platinum Pt - 0,29; platinum dichloride tl2- 0,04; rhenium Re - 0,56; media - 99,11.

The molar ratio of Pt:PtCl2=9:1.

The catalysts synthesized in examples 1, 2 and 3, was tested for activity in the catalytic reforming process faction 85-180°at pilot plant developed by Vniineftehim for testing catalysts for reforming of gasoline fractions. Conditions and results of tests of the catalysts shown in the table.

The catalyst is made the value of the octane number by the motor method (MM) stabil the aqueous reformate.

The table also shows the results of comparative testing of the industrial catalyst Ref-23 (prototype). The table shows that in the whole range of investigated temperatures of process catalysts synthesized in examples 1, 2 and 3 exceed the activity of the catalyst Ref-23.

Table

The results of the test catalysts reforming
Name catalystPressure, MPaThe volumetric feed rate, h-1The ratio of hydrogen to the raw material, the IO/lTemperature, °Duration of test, hours.The octane number by the motor method)
Ref-232,51,51500:14704880.2
2.51.51500:14802482.4
2.51.51500:14902484.6
For example 12,51,51500:14704885.3
2.51.51500:148024 87.5
2.51.51500:14902488.6
For example 22,01,51500:14704896,0
2.01.51500:14802499,0
2.01.51500:14902499,9
For example 32,01,51500:14704881,0
2.01.51500:14802485,0
2.01.51500:14902491,0

1. The catalyst for reforming of gasoline fractions containing platinum and rhenium oxide on the carrier, characterized in that as the carrier is alumina, where the content of oxides of sodium, iron and titanium limited: Na2O - not more than 5 ppm; Fe2O3- not more than 20 ppm; TiO2not more than 2000 ppm, as platinum is part of the catalyst is restored in the metallic state in the form dichloride boards who are at a molar ratio of platinum restored in the metallic state and platinum dichloride Pt:PtCl 2=9:1÷1:1 in the following ratio, wt.%:

Platinum (Pt) 0,13-0,29

Dichloride, platinum (PtCl2) of 0.18 to 0.04)

Rhenium (Re) 0,26-0,56

The media (Al2About3) 99,43-99,11

2. The preparation method of the catalyst for reforming of gasoline fractions, including the impregnation of the carrier - oxide aluminum compounds of platinum and rhenium, drying, calcining and recovery, characterized in that the alumina is impregnated with a joint solution of hexachloroplatinic acid, ammonium perrhenate, acetic and hydrochloric acids, followed by drying and annealing with simultaneous recovery of 50-90% of platinum in the temperature range 160-550°With the rise of temperature from 160 to 280°C for 30-60 min by creating under these conditions, the annealing reducing atmosphere due to the rapid decomposition of ammonium acetate formed during the preparation of joint impregnating solution.



 

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11 cl, 4 dwg, 3 tbl, 16 ex

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4 cl, 1 tbl, 8 ex

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