A method of processing hydrocarbon feedstock and the catalyst for its implementation

 

(57) Abstract:

The present invention relates to catalytic processing of hydrocarbons and catalyst for the process. Essence: carbon raw material is processed in the presence of a catalyst containing, wt.%: zeolite type WHC, DCM, ZSM-5, ZSM-8, ZSM-11 with silicate module 30-100 - 50,0-80,0, Zn or Ga in terms of the metal - 0,5-5,0, alumina obtained from aluminum hydroxide formed by thermochemical decomposition of the aluminate materials, a promoter selected from the group of Cl, F, Mg, Ca, Sn, IN2O3or their mixture, a total of not more than 1.0, an impurity selected from the group of Na2O, Fe2O3, or a mixture of a total of not more than 0.7, the alumina - rest. Use of hydrocarbon raw materials, composition, wt.%: paraffins C1-C13(n - and ISO - total) 2,7-99,5, aromatic hydrocarbons6-C12no more than 25,0, naphthenes, C5-C12no more 38,0, dieny4-C6not more than 3.0, acetylene hydrocarbons not more than 0.85, aliphatic alcohols C1-C6and their ethers, in total not more than 0,5, nitrogen-containing compounds in total in terms of nitrogen not more than 0.1, sulfur-containing compounds in total in terms of sulphur not more than 0.7, to hydrocarbons with various olefins and paraffins without deep separation of impurities from raw materials and separation of the feedstock. 2 N. p. F.-ly, 3 tables.

The invention relates to the technology of organic synthesis, namely, catalytic methods of processing of hydrocarbon raw materials to produce products, which can be used either directly as motor fuel or as a component of a fuel or as raw material for separation of aromatic hydrocarbons and a catalyst for the implementation of these methods.

Known methods of processing of hydrocarbon raw materials to produce aromatic hydrocarbons and flavored gasoline by contact with a heterogeneous zeolite catalysts containing zeolites of type pentasil (ZSM, WHC, DCM, ultrasil and so on), which in addition to zeolites contain metallic components Ni, Co, Mo, W, Cd, Zn, Ga and binder - Al2O3/Minachev H. M., A. Dergachev, A. Aromatization of paraffins in the zeolite family Pancasila. USP, 1990, I. 59, No. 9. - S. 1522; A. H. Dorogochinskii and other low molecular paraffin Aromatization of hydrocarbons on zeolite catalysts, Tsniiteneftehim, Petrochemistry and sleeperette, M., 1989. 84 C./. The greatest popularity and effectiveness are ways aromatization of C2-C5+-paraffins catalytic systems is atenololo raw materials.

Known methods of processing of hydrocarbon raw materials to produce high-octane gasoline using catalysts containing high zeolites of type ZSM and their domestic counterparts /RF patents №2112013, 1998; No. 2117030, 1998; No. 2123514, 1998/. In these methods, the contacting with the catalyst is subjected to only registersee raw materials, mainly gas WITH2-C5+-olefinic fraction. Use of Zn-containing catalysts based on zeolite ZSM-5, ZSM-8, WHC, the CVM. As a binder in the above catalysts are used-Al2O3received nitrate-aluminate way.

The disadvantage of these methods of processing hydrocarbon material is the inability to efficiently process raw materials containing both olefins and paraffins.

The closest in technical essence and inventive step is a method of processing hydrocarbon feedstock and the catalyst described in patent RF №2159268, 2000 In this way the contact with the zeolite catalyst is subjected to a wide fraction of the hydrocarbon, C2-C5.

The above method allows to obtain high octane gasoline from the technical fraction2-ptx2">Compounds of sulfur, Not more than 0,5

Water Not more than 0.2

Ethers, Not more than 0.005

Ethanol and methanol Not more than

of 0.05 total

Amines Not more than 0,01

Acetylene

the hydrocarbon Traces

Alkanes and hydrocarbons WITH5+No more than 15 total

Alkanes WITH3-C4Else

To implement the process using the catalyst composition, wt.%:

high-silica zeolite (WHC, DCM, ZSM-8, ZSM-5 with silicate module 30-80) 50 80, zinc 0.5 to 5, the alumina - rest. The process is carried out at a volumetric feed rate of the raw material 1 6 h-1temperature 230 560 C, a pressure of 0.1 to 2.0 MPa.

The main disadvantages of the method include the need for separation (separation, dilution) from a feedstock impurities catalytic poisons - hydrocarbons WITH5+(to the level of not more than 0.1 wt.%), sulfur (up to a level of not more than 0.01 wt.%), dienes (up to 0.25 wt.%) and the focus of the method, mainly for processing of olefinic materials.

The aim of the present invention is to provide a process and catalyst for the hydrocarbon processing with various olefins and paraffins without deep separation of impurities from raw materials and separation of the feedstock.

ora containing high-silica zeolite with silica module 30-100 type WHC, DCM, ZSM-5, ZSM-8, ZSM-11, Zn or Ga, alumina obtained from aluminum hydroxide formed by thermochemical decomposition of the aluminate raw material containing a promoter selected from the group of Cl, F, M, g, a, S, n2ABOUT3or their mixture, impurities selected from the group of Na2O, Fe2ABOUT3or their mixture in the following ratio, wt.:

Zeolite type WHC, CVM,

ZSM-5, ZSM-8, ZSM-11

with silicate module

30-100 50,0-80,0

Zn or Ga in terms of

metal 0,5-5,0

A promoter selected from the group

Cl, F, Mg, Ca, Sn, IN2ABOUT3

or a mixture of a total of Not more than 1,0

Impurities selected from the

group Na2O, Fe2ABOUT3or

a mixture of a total of Not more than 0.7

Alumina Rest

using hydrocarbon composition, wt.%:

Paraffins1-C13

(n - and ISO-total) 2,7-99,5

Aromatic hydrocarbons

WITH6-C12No more than 25,0

Naphthenes, C5-C12No more 38,0

Dieny4-C6Not more than 3.0

Acetylene hydrocarbons Not more than 0.85

Aliphatic organisations

Total in terms of

nitrogen is Not more than 0.1

Sulfur containing compounds

Total in terms of

sulphur Not more than 0.7

Water Not more than 0,5

Olefins WITH2-C8Else

Preferably the process is carried out at a temperature 230-590 C, a pressure of 0.1-2.0 MPa, the space velocity of the raw material in terms of the liquid is 0.5 to 10.0 h-1.

The above objective is also achieved by the creation of catalyst processing of hydrocarbon raw material containing high-silica zeolite with silica module 30-100 type WHC, DCM, ZSM-5, ZSM-8, ZSM-11, Zn or Ga, alumina obtained from aluminum hydroxide formed by thermochemical decomposition of the aluminate raw material containing a promoter selected from the group of Cl, F, Mg, Ca, Sn, IN2O3or their mixture, impurities selected from the group of Na2O, Fe2ABOUT3or their mixture in the following ratio, wt.:

Zeolite type WHC, DCM, ZSM-5, ZSM-8, ZSM-11

with silicate module 30-100 50,0-80,0

Zn or Ga in terms of metal 0,5-5,0

A promoter selected from the group

Cl, F, Mg, Ca, Sn, IN2ABOUT3or their mixture, in total Not more than 1,0

Impurities selected from the group

Na2O, Fe2O3the amount which I use in the described catalyst of aluminum oxide, derived from the hydroxide produced by thermochemical decomposition of the aluminate material. Technology for the production of aluminum hydroxide for catalyst includes the following stages:

- drying technical aluminum hydroxide (three-hydrate or hydrargillite);

- thermodispersion aluminum hydroxide;

- hydration and rinsing of the product thermodispersion;

- thermoactivation (autoclaving), obtaining a suspension of aluminum hydroxide;

- evaporation and adjustment of the pH of a suspension of aluminum hydroxide.

At the stage of drying technical aluminum hydroxide is subjected to a drying process in a distribution dryer at a temperature of 320-400 With removal of surface and 3-8% of structural moisture.

Under thermodispersion destroyed the crystal structure of three-hydrate or hydrargillite obtaining x-ray amorphous alumina product. Stage is carried out in a spray drier at a temperature of 370-420 C.

Stage hydration and rinsing of the product thermodispersion ensures removal of excess water-soluble impurities, including impurities of sodium, and swelling of the alumina product. Stage autocl the slots at a temperature of 120-160 With the obtained semi-finished product, requiring evaporation and adjustment of pH.

Evaporation mass obtained by autoclaving, adjusted pH to the desired value, as determined by the technology of production of the final catalyst, leads to the production of the raw material aluminum hydroxide with humidity 50-82%, suitable for the preparation of the catalyst compositions.

Derived from the hydroxide oxide of aluminum compared to bemany analogue has a regular porous structure, especially in combination with zeolites, which contributes to the controllability of the process, especially at the stages of the synthesis, activation and regeneration of the catalyst, the reduction of coke formation at elevated temperatures of the process.

The main composition of the catalyst, the presence of certain promoters, as well as their absence, the permissible limit of impurities determined empirically, and on the basis of the underlying regularities in catalysis carried out on various types of raw materials containing different classes of hydrocarbons and non - hydrocarbonaceous impurities catalytic poisons.

As raw materials for the implementation of the proposed method using technical hydrocarbon fractions, the composition of which is given in the table. 1.

moulding, by drying and calcining to obtain the composition shown in table. 2.

An example of the preparation of the catalyst

To 137,5 kg pellets of aluminum hydroxide (with a humidity of 80%) add 140 kg of zeolite computers in NH+4form with silicate module 50 (with a humidity of 50% and 11.5 kg of zinc nitrate Zn(NO3)26N2O based on a 2.5% Zn).

The catalyst composition is stirred to bring the pH to a value of 4.5 to 5.0 with aqueous ammonia (NH3aq) and evaporated to formemost (humidity 55%).

The catalyst mass is formed into pellets with a diameter of 2.5-3.0 mm, dried at a temperature of 120-140 With 6-8 hours (to a moisture content of 20-30%), calcined at a temperature of 500-550 C for 4-8 h in a current of dry air. The calcined catalyst scatter from dust and crumbs, stariway.

At the stage of formation of the catalyst composition in weight can be entered promoting components, salts, oxides or acids in crystalline form or in an aqueous solution containing promoters catalyst Cl, F, Mg, Ca, Sn, B(B2O3).

In order to obtain comparative data more closely similar experiments carried out on installation and conditions of this analogue:

- pre-proactively catalyst assistanteditor execute (if necessary) for 3-5 hours at a temperature of 450-540;

- regeneration zakoksovanie catalyst is carried out after the completion of the process of synthesis under the conditions: temperature 250-595 With, the oxygen content of the regenerating mixture of 0.5-5 vol.%, the ratio of nitrogen-air mixture: water vapor is 1:0.01 to 0.5 wt.

The results of the experiments - implementation of a method of catalytic hydrocarbon processing are presented in table. 3.

As can be seen from the results table. 3, the resulting liquid products of experiments№№4, 5, 7, 8, 10, 19 are components of motor fuels; liquid products of experiments No. 9, 11-16, 21 components and automotive fuels directly with the appropriate octane number; products of experiments№№1-3, 6, 17, 23, 25 - aromatic components of gasoline (limited) and mainly raw materials for separation of aromatic hydrocarbons.

The data table. 3 (comparative experiments№№18, 20, 22, 24, 26 and№№17, 19, 21,23, 25 - the described method show:

- deeper aromatizes the ability of the catalyst of the present invention, resulting in increased octane number of the final product;

- longer mainegenealogy mileage catalyst of the present invention;

- ability with the use of the above catalyst effecticely the final liquid product.

In General, the described method and the catalyst can be used in oil and gas production, oil refining, petrochemical and organic synthesis for processing of various hydrocarbons, preferably light - from gas to liquid (liquid) wax - and registergui oil and gas fractions of primary and secondary origin.

1. A method of processing hydrocarbon material in the presence of a catalyst containing high-silica zeolite, a metal component, the aluminum oxide at elevated temperature and pressure, characterized in that the use of catalyst containing high-silica zeolite with silica module 30-100 type WHC, DCM, ZSM-5, ZSM-8, ZSM-11, as a metal component containing Zn or Ga, as of alumina - alumina obtained from aluminum hydroxide formed by thermochemical decomposition of the aluminate materials, and optionally containing a promoter selected from the group of Cl, F, Mg, Ca, Sn, IN2ABOUT3or their mixture, impurities selected from the group of Na2O, Fe2O3or their mixture in the following ratio, wt.%:

Zeolite type WHC, DCM, ZSM-5, ZSM-8, ZSM-11

with CL, F, Mg, Ca, Sn, IN2ABOUT3

or their mixture, in total Not more than 1,0

Impurities selected from the group of Na2O, Fe2ABOUT3

or their mixture, a total of Not more than 0.7

Alumina Rest

and as of hydrocarbon raw materials used raw materials composition, wt.%:

Paraffins C1-C13(n - and ISO - total) 2,7-99,5

Aromatic hydrocarbons WITH6-C12No more than 25,0

Naphthenes, C5-C12No more 38,0

Dieny4-C6Not more than 3.0

Acetylene hydrocarbons Not more than 0.85

Aliphatic alcohols C1-C6and their

ethers, in total Not more than 0,5

Nitrogen-containing compounds, total,

in terms of nitrogen Not more than 0.1

Sulfur-containing compounds, total,

in terms of sulphur Not more than 0.7

Water Not more than 0,5

Olefins WITH2-C8Else

2. The method according to p. 1, wherein the process is carried out at a temperature of 230-C, a pressure of 0.1-2.0 MPa, the space velocity of the raw material in terms of the liquid is 0.5 to 10.0 h-1.

3. The catalyst for the processing of hydrocarbon raw material containing high-silica zeolite, a metal component, the aluminum oxide is, SM-11, as the metal component contains Zn or Ga, as of alumina-alumina obtained from aluminum hydroxide formed by thermochemical decomposition of the aluminate raw material, and further comprises a promoter selected from the group of Cl, F, Mg, Ca, Sn, IN2ABOUT3or their mixture, impurities selected from the group of Na2O, Fe2O3or their mixture, in the following ratio, wt.%:

Zeolite type WHC, DCM, ZSM-5, ZSM-8,

ZSM-11 with silicate module 30-100 50,0-80,0

Zn or Ga in terms of metal 0,5-5,0

A promoter selected from the group of Cl, F, Mg,

Ca, Sn, IN2ABOUT3or their mixture, in total Not more than 1,0

Impurities selected from the group of Na2O, Fe2O3,

a total of Not more than 0.7

Alumina Rest

 

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