The catalyst for the conversion of aliphatic hydrocarbons* 002-*001*002 in high-octane component of gasoline, is enriched in aromatic hydrocarbons

 

(57) Abstract:

The invention relates to a zeolite-containing catalysts for the conversion of aliphatic hydrocarbons, C2-C12in high-octane gasoline or aromatic hydrocarbons. The catalyst contains a group zeolite with SiO2/Al2O3= 20oC80 mol/mol with a residual content of Na2O of 0.1-0.4 wt.%, a binder component, zinc and a mixture of oxides of rare earth elements in the following ratio of components (wt.%):

Zeolite - 25,0-50,0

Zinc - 1,0-3,0

The sum of the oxides of rare earth elements - 0,1-2,0

Binder - the Rest,

where the oxides of rare earth elements have the following composition (wt.%):

CeO2- 40-55

The amount of La2O3Pr2O3Nd2O3- 60-45

The use of the catalyst composition mixture of rare earth elements leads to an increase in the yield of aromatic hydrocarbons in the process of aromatization of hydrocarbons. 3 table.

The invention relates to the composition of zeolite catalysts for the conversion of aliphatic hydrocarbons, C2-C12contained in low-octane gasoline, wide fraction of light hydrocarbons, paynow are high zeolites groups of pentelow ZCM-5, ZCM-11, DCM, WHC and others. The content of zeolite in the catalyst varies widely (1 to 99 wt.), and as the binder typically use aluminum oxide of the gamma-Al2O3silica, aluminosilicates.

As a promoter, increases the activity of the catalyst in the aromatization reactions, various methods of introducing metals or metal oxides. The content of the promoters in the catalyst is generally 0.1-10%

The most effective promoters of aromatization catalysts are Zn and Ga [1] however, Ga scarce and expensive metal.

The disadvantage of zinc-containing catalysts is irreversible reduction of their activity as a result of ablation of zinc in the conditions of high temperature reaction and catalyst regeneration. To reduce the loss of zinc in the catalyst to impose an additional one or more metals Ga [1] groups IB, VIII, [2, 3] or rare earth elements (REE) [3]

In some cases, the presence of the second metal in the zinc-containing zeolite catalyst increases the yield of aromatic hydrocarbons in the conversion of gases. This effect is observed with the introduction of Ga [1] Au, Pt, Ag [3] it is also Known positive effect of REE on containing Ga zeolite is correspondingly increase the conversion of paraffins C2- C4and the selectivity of the process for aromatic hydrocarbons with the introduction of a catalyst containing 0.2 to 1.0 wt. Ga, at least one of rare earth elements in an amount of 0.1-2.0 wt.

Closest to the proposed catalyst for aromatization of aliphatic hydrocarbons, C2-C12is the catalyst described in [3] Patented zeolite catalyst contains zinc and a metal from the following range: group IB and VIII of the Periodic system, Ge, Re, REE. The total metal content in the catalyst is 0.1-10 wt. Patented the catalyst containing 0.1-5.0 wt. Zn and 0.1-2.0 wt. metal from the specified number. Metals are introduced into the catalyst by any known method.

The task that sent the claimed technical solution is to create a catalyst for aromatization of aliphatic hydrocarbon-based group of zeolites pentelow that do not contain expensive and scarce metals, with increased activity in the formation of aromatic hydrocarbons and having high selectivity in the formation of hydrocarbons C5+.

The required technical result is achieved by the fact that the catalyst for the conversion of aliphatic hydrocarbons, C2-C12in high-octane to the ratio of SiO2/Al2O3=20oC80 with a residual content of sodium oxide is 0.1-0.4. zinc, a binder component and a rare earth element, in which the catalyst contains a mixture of 40-55 wt. cerium oxide, 45-60 wt. the sum of the oxides of lanthanum, praseodymium and neodymium in the following ratio, wt.

Zeolite 25,0-50,0

Zinc 1,0-3,0

Rare earth element of 0.1-2.0

Binder is the Rest

As a binder can be used alumina, aluminosilicates, clay and other suitable for this purpose connection.

The proposed composition of the catalyst differs from the known fact that the zeolite catalyst containing zinc is introduced a mixture of oxides of rare earth elements CeO2La2O3Pr2O3and Nd2O3. The observed effect of the increase in the yield of aromatic hydrocarbons in the process of aromatization of aliphatic hydrocarbons due to strong promoting effect in the introduction instead of one rare earth material four.

The catalysts can be prepared in different ways and to different method of granulation of the zeolite with a binder, the method of introduction of the metal promoters in chotoviny catalyst and with an equal amount of the promoting components zinc oxide is one of the rare earth metal prototype and zinc and offer a mixture of oxides of rare earth metals according to the invention the proposed activity of the catalysts in the formation of aromatic hydrocarbons from aliphatic feedstock above, and to obtain high-octane gasoline of low octane higher yield of liquid hydrocarbons.

Below are examples of the preparation of the catalysts of the proposed composition and the results of their testing in the conversion of low-octane gas condensate gasoline and light hydrocarbon fraction in the high-octane components of gasoline.

Example 1. For the preparation of a catalyst mass in the mixer load 20 l of condensate and 1400 g of water pellet of aluminum hydroxide (SPT 8 wt.) and after stirring for 0.5 h to obtain a homogeneous suspension. Then in the device add a solution of 70.7 g azotnokislogo zinc Zn (NO3)2x6H20 in 1 l of condensate and solution of 80 g of a mixture of ototoxicity salts of rare earth elements in 0.4 l of condensate. After stirring for one hour in a mixer add 457.5 g of zeolite CVMS (SPT-15 wt.). The suspension is stirred at normal temperature for 0.5 h, and then increase the temperature to 50-60oC and incubated catalyst mass for 3 hours Then starecheski catalyst particles, exposed after the calcination at 550oC for 6 h in a boiling layer, expected air. Catalysts obtained diffuse emitting faction 0,056-0,315 mm.

The catalysts according to examples 2-8 were prepared similarly to the catalyst of example 1. The number of the blend components were taken from a composition prepared catalysts are shown in table.1.

Specified in the table.1 the ratio of REE oxides in the catalysts was obtained by calcination of the catalysts activated with a solution of nitrate salts REE (concentration 200 g/l), with the corresponding ratio of REE oxides. The content of impurities in the solution of salts of rare-earth elements, wt. on the REE oxides:

CaO 8,1

Na2O 11,0

Fe2O30,2

Used in the composition of the catalysts zeolites computers, CWMS and computers have the following characteristics:

The molar ratio of SiO2/Al2O320-80

The content of Na2O, mass. 0,1-0,4

The degree of crystallinity by x-ray phase analysis, Rel. Not less than 95

Static capacity, cm3/g

water Not more than 0.08

the heptane is Not less than 0,20

In table. 1 the compositions of the catalysts prepared according to examples 1-5, soo is as a binder component of the catalysts used aluminum oxide (for preparation of a catalyst mass of water pellet aluminum hydroxide) and synthetic aluminosilicate (as).

Samples of the resulting catalysts were tested in the pilot installation on various types of raw materials in the turbulent regime fluidized catalyst under given conditions for 2 hours without regeneration.

Test conditions: reactor pressure of 0.5 MPa, a temperature of 480 - 550oC, the volumetric flow rate of gasoline 3 h-1, NGL 200 h-1.

The raw material used wide fraction of light hydrocarbons and a gasoline fraction of gas condensate. The composition of raw materials are given in table. 2.

The results of the testing of the catalysts are given in table. 3, indicates an increase in the activity of zeolite catalysts containing the oxides of Zn, with the introduction of their composition instead of the oxides of Ce or La on a mixture of oxides of rare-earth elements, and the effect is greater at higher REE content in the catalyst.

The catalyst for the conversion of aliphatic hydrocarbons, C2- C12in a high-octane component of gasoline, is enriched in aromatic hydrocarbons containing group zeolite with a molar ratio of SiO2/Al2O320 80 residual content of sodium oxide is 0.1 to 0.4 wt. zinc, rare earth element and a binder component, wherein as is risetime and neodymium in the following ratio of components, wt.

Zeolite 25 50

Zinc 1 3

Rare earth element 0,1 2,0

A binder component Ostalnoe

 

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