The catalyst for the conversion of aliphatic hydrocarbons2-c6and how transformations of aliphatic hydrocarbons2- c6in high-octane gasoline or aromatic hydrocarbons

 

(57) Abstract:

The invention relates to catalysts for the conversion of aliphatic hydrocarbons, C2- C6in high-octane gasoline or aromatic hydrocarbons, as well as to methods of transformation of aliphatic hydrocarbon, C2- C6in high-octane gasoline or aromatic hydrocarbons. The catalyst contains a zeolite type pentasil with silicate module SiO2/Al2O3= 35 - 50 60-75 wt.%, modifier - fluoride zinc 1,4-4.6 wt.%, which is injected a mixture of fluoride zinc zeolite, and binder - aluminum oxide - the rest up to 100 wt.%. The process is carried out at a temperature 280-550oC, a pressure of 0.15-2.0 MPa and space velocity of the gaseous raw material 360-1200 h-1. The catalyst has high activity, selectivity and stability. 2 c.p. f-crystals, 2 tab.

The invention relates to the refining and petrochemical industries, in particular to methods of obtaining efficient processing catalysts aliphatic hydrocarbon, C2-C12in high-octane gasoline or concentrate of aromatic hydrocarbons.

Known zeolites family Pancasila, modified by various meta the zine or aromatic hydrocarbons [see thematic review A. H. Dorogochinskii, A. L. Proskurnin, S. N. Ovcharov, N. N. Krupin "Aromatization of low molecular weight paraffin hydrocarbons on zeolite catalysts".- M: 1989.- # 4.-84 C.], the disadvantages of which are either high cost modifiers, or the complexity of the ways of their introduction into the zeolite, or a short period mejregionalnoi work, leading to frequent regeneration.

The closest to the essence of the technical solution is the catalyst for conversion of hydrocarbons, C3-C4in high-octane gasoline or aromatic hydrocarbons, comprising the zeolite of type pentasil with silicate module SiO2/Al2O3=35-40, the binder component and the modifiers - zinc and silicon fluoride [see RF patent N 95121235, M. pl. BI N 33, 1997] in the following, wt.%:

Zeolite H-ZSM-5 - 65-75

Zinc - 1,8-2,2

Silicon-fluoride - 0,25 - 3,75

Binding - Rest

Use of this catalyst for the conversion of aliphatic hydrocarbons, C3-C4in high-octane gasoline or aromatic hydrocarbons is recommended for the following parameters of the technological mode: temperature 280 - 450oC, a pressure of from 0.3 to 1.0 MPa, the space velocity of the feed gaseous VA modifiers (zinc, silicon-fluoride) to obtain stable catalyst transformations of aliphatic hydrocarbons3-C4in high-octane gasoline or aromatic hydrocarbons; separate modification of the catalyst leads to an increase in the number of stages of its production, i.e., the complexity catalyst production, and consequently increase the cost of the catalyst; introducing modifiers gradually leads to an additional amount trudnoozhidaemyh wastewater generated during the modification and subsequent leaching of the catalyst.

The technical result - the reduction of the number of modifiers catalyst intended for the conversion of aliphatic hydrocarbons2-C6in high-octane gasoline or aromatic hydrocarbons; eliminating the use of expensive and scarce modifiers; use of simple and cheap way simultaneous administration of zinc and fluorine in the zeolite method of mixing fluoride zinc zeolite before the stage of granulation with a binder; reduction of process operations associated with obtaining effective penicillinases catalyst transformations of aliphatic hydrocarbons2-C6

The essence of the invention.

1. By introducing the zeolite simultaneously fluorine and zinc can be obtained bifunctional catalyst capable of providing a high yield of high octane gasoline or aromatic hydrocarbons from aliphatic hydrocarbons, C2-C6for quite long periods basegenerated work. If you enter modifiers separately, the production process of the catalyst will become more complicated and its cost will increase. Therefore, the use of fluoride zinc ZnF2produced on an industrial scale, will allow for the simultaneous modification of zeolite zinc and fluoride.

Because fluoride zinc - soluble salt, the traditional methods of ion exchange and impregnation for modifying zeolite unusable. Therefore, for the joint modification was applied to more simple and cheap method of directly mixing the zeolite with a salt followed by granulation of a mixture of ways: decationization original powdered zeolite type pentasil with silicate module SiO2/Al2O3=35-50 exercise twice treated with a solution of ammonium nitrate of 0.5 N. the concentration of 20 l per 1 kg of zeolite. The exchange of sodium ions with ammonium carried out by heating to a temperature of 60-70oC and stirring for 3 hours.

After washing the zeolite from the nitrate anion hot distilled water, it was subjected to drying first at a temperature of 50-70oC for 5-6 hours, and then for two hours at 120oC. decomposition of the ammonium form of the zeolite is carried out at a temperature of 550oC for 3-4 hours. Re-process the zeolite carry out the same quantity of a solution of ammonium nitrate with a repetition of all subsequent stages.

Zinc-containing catalyst produced by the method of mixing the powder decationizing of zeolite and zinc fluoride with aluminum oxide at the stage of forming.

The right amount of salt (zinc fluoride) is determined by the formula

< / BR>
where Me is a metal, introduced into the zeolite, wt.%;

Gpthe amount of zeolite, g;

MIU, Msaltmolecular weight according to the input metal salt,

The aluminum oxide at the stage of forming pre-expose patisaul, the granules are dried at a temperature of 20-50oC for 12 hours, then at a temperature of 120oC for 2-3 hours.

The content of components in pentecostarion catalyst following, wt. %:

Zeolite - 60 - 75

Fluoride zinc - 1,4 - 4,6

Binding - Rest

Example 1.

To prepare 100 kg of catalyst (Zn-NCVM-1) containing 2 wt.% Zn on the zeolite and 60 wt.% zeolite take 60 kg of zeolite type pentasil brand computers with silicate module SiO2/Al2O3=43,7. Decationization exercise twice treated with a solution of ammonium nitrate of 0.5 N. the concentrations in the amount of 1200 l to the processing rate of 20 liters per 1 kg of zeolite. The exchange of sodium ions with ammonium carried out by heating to 60oC and stirring for 3 hours.

After washing the zeolite from the nitrate anion hot distilled water, it was subjected to drying first at a temperature of 50-70oC for 5 hours, and then for two hours at 120oC. decomposition of the ammonium form of the zeolite is carried out at a temperature of 550oC for 4 hours. Re-process the zeolite carry out the same quantity of a solution of ammonium nitrate with a repetition of all subsequent stages.

aluminum led quantity 38,06 kg is subjected to peptization of concentrated nitric acid, then mixed with the zeolite and ZnF2. The resulting mass granularit, granules dried at 25oC 12 hours, and then at a temperature of 120oC for 3 hours. After drying, the catalyst prior to use in the process of converting aliphatic hydrocarbon, C2-C6calcined in air flow at a temperature of 550oC 5 hours.

The content of components in pentecostarion catalyst (Zn-NCVM-1) as follows, wt.%:

Zeolite - 60

Fluoride zinc - 1,94

Binder - 38,06

Example 2.

To prepare 100 kg of catalyst (Zn-NCVM-2), containing 5 wt.% Zn on the zeolite and 60 wt.% zeolite take 60 kg of zeolite type pentasil brand computers with silicate module SiO2/Al2O3=43,7. Decationization exercise twice treated with a solution of ammonium nitrate of 0.5 N. the concentrations in the amount of 1200 l to the processing rate of 20 l per 1 kg of zeolite. The exchange of sodium ions with ammonium carried out by heating to 60oC and stirring for 3 hours.

After washing the zeolite from the nitrate anion hot distilled water, it was subjected to drying first at a temperature of 50-70oC for 5 hours, and then for two hours at 120oC. Razlozhenia carry out the same quantity of a solution of ammonium nitrate with a repetition of all subsequent stages.

Dried dictionary-type zeolite DCM mixed with a powder of a fluoride zinc in the amount of

< / BR>
The aluminum oxide in the amount of 35,01 kg is subjected to peptization of concentrated nitric acid, then mixed with the zeolite and ZnF2. The resulting mass granularit, granules dried at 25oC 12 hours, and then at a temperature of 120oC for 3 hours. After drying, the catalyst prior to use in the process of converting aliphatic hydrocarbon, C2-C6calcined in air flow at a temperature of 550oC 5 hours.

The content of components in pentecostarion catalyst (Zn-NCVM-2) the following, wt%:

Zeolite - 60

Fluoride zinc - 4,99

Binder - 35,01

2. Through the use of pentasaccharides catalyst, simultaneously modified zinc and fluorine, will increase the period mejregionalnoi operation of the catalyst by reducing the speed of the process of coke formation in his presence that will increase the performance of the installation. This method of simultaneous modification of the catalyst, zinc and fluoride by the method of mixing the zeolite with a salt of a simple and cheaper than traditional methods of impregnation and ion exchange.glendorado C2-C6in high-octane gasoline or concentrate of aromatic hydrocarbons. Transformation of aliphatic hydrocarbon, C2-C6in high-octane gasoline or aromatic hydrocarbons in the presence of this catalyst may be carried out in the temperature range 280-550oC, pressure of 0.15-2.0 MPa and space velocity of the gaseous raw material 360-1200 h-1.

A specific example of the method of transformation of aliphatic hydrocarbon, C2-C6: depending on the purpose of processing aliphatic hydrocarbon, C2-C6temperature varies. If the processing of aliphatic hydrocarbon, C2-C6containing significant amounts of olefins, carried out with the aim of producing high octane gasoline containing a small amount of aromatic hydrocarbons, the optimal conditions for its implementation in the presence of the proposed catalysts are:

temperature - 280 - 350oC,

pressure of 0.15-2.0 MPa,

the volumetric feed rate of the gaseous raw material - 360-1200 h-1.

If the processing of aliphatic hydrocarbon, C2-C6performed with the purpose of agemy catalysts will be:

temperature - 500 - 550oC,

pressure of 0.15-2.0 MPa,

the volumetric feed rate of the gaseous raw material - 360-1200 h-1.

When the process of transformation of aliphatic hydrocarbon, C2-C6in the temperature range 350 - 500oC turns out high-octane gasoline with a high content of aromatic hydrocarbons.

A special feature of this process can be called the stability of the quality of gasoline octane numbers and chemical composition, as well as the stability of the component composition of the resulting aromatic hydrocarbons throughout the cycle mejregionalnoi operation of the catalyst, and after the regeneration. Recommended regeneration of the catalyst - nitrogen-air (oxidative type) with Viigo comsomoliste substances at 540-560oC. the Catalyst restores its activity after regeneration completely. The duration of the mileage between regenerations 400 hours Working pressure is determined either by the hydraulic resistance of communications and reactor site, or the interests of the customer. Warranty period of operation of the catalyst at least one year.

Example 3.

Object of research are the two the AI in the presence of a catalyst Zn-NCVM-2 was carried out with the aim of producing high octane gasoline with a low content of aromatic hydrocarbons (up to 15 wt.%) at temperatures of 300-350oC. the Results are shown in table. 1.

Example 4.

The object of the study was the propane-propylene fraction from the catalytic cracking process. Conversion of propane-propylene fraction in the presence of a catalyst Zn-NCVM-2 was carried out with the purpose of obtaining a concentrate of aromatic hydrocarbons at temperatures of 500-550oC. the Results are shown in table.2.

Application for the conversion of aliphatic hydrocarbons, C2-C6in high-octane gasoline or aromatic hydrocarbons panchasilanyasa catalysts developed on the presented methodology will simplify the way of getting active, selective and stable catalyst, and reduce the amount of effluent from the catalyst production. Increase mezhregionalnogo period will reduce the number of regenerations of the catalyst, which in turn will increase the productivity of plants intended for processing aliphatic hydrocarbon, C2-C6to

1. The catalyst for the conversion of aliphatic hydrocarbons, C2- C6in high-octane gasoline or aromatic hydrocarbons, is eat, the zeolite type pentasil has silicate module SiO2/Al2O3= 35 - 50 as a modifier catalyst contains fluoride zinc and the introduction of the modifier is carried out by mixing the fluoride zinc zeolite with the following content of components in the catalyst, wt.%:

Zeolite - 60 - 75

Fluoride zinc - 1,4 - 4,6

Binding - Rest

2. The method of transformation of aliphatic hydrocarbon, C2- C6in high-octane gasoline or aromatic hydrocarbons in the presence of a catalyst comprising the zeolite of type pentasil, modifiers and zinc fluoride, junction - alumina, wherein the used catalyst under item 1 and the process is carried out at a temperature of 280 - 550oC, a pressure of 0.15 - 2.0 MPa and space velocity of the gaseous raw material 360 - 1200 h-1.

 

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