Method of producing high octane gasoline fractions and aromatic hydrocarbons

 

(57) Abstract:

Usage: in the petrochemical industry. The feedstock is contacted in the presence of hydrogen at temperatures of 280 - 460oC (preferably 320 to 440oC) and a pressure of 0.1 - 4.0 MPa (preferably 0.5 to 2 MPa) with a catalyst containing ZSM-5 or ZSM-11 General empirical formula (0,02 - 0,09)Na2O Al2O3(0,01 - 1,13)Fe2O3(27 - 212)SiO2kH2O modified the elements or compounds of elements of V, VI, VII group, in the amount of 0.05 - 5.0 wt.% or zeolite General empirical formula where enABOUTm- one or two oxide elements II, VI and VIII groups, and k is the corresponding capacity factor, or zeolite General empirical formula where enOm- one or two oxide elements II, III, V and VI groups, and k is the corresponding capacity factor, modified by the elements or compounds of elements I, II, IV, V, VI, VII and VIII groups in the amount of 0.05 - 5.0 wt.%, with the subsequent separation of the products contacting gaseous and liquid fractions. Raw material process can be hydrocarbons WITH2- C12and their fractions and/or oxygen-containing organic compounds (alcohols, esters, etc. and mixtures thereof. The technical result - the reduction temperature proteoid to methods for unleaded high-octane gasoline fractions and/or aromatic hydrocarbons from hydrocarbon and/or oxygen-containing organic compounds.

Raw material process can be a hydrocarbon, C2-C12and their fractions and/or oxygen-containing organic compounds (alcohols, esters, etc. and mixtures thereof.

Currently unleaded high-octane gasoline is produced by compounding virgin and secondary gasoline with a high octane components (including aromatic hydrocarbons), obtained by different refining processes [Gureyev, A. A., Zhorov Y. M., Smidovich E. C. Production of high-octane gasoline. - M, - Chemistry, 1981, - 224 C.]. Therefore, in General, the technology of obtaining trademark high-octane unleaded gasoline is quite complex. In connection with the creation of the family of zeolites pentasil with the structure of ZSM-5, ZSM-11 (General formula nNa2OAl2O3/mSiO2where n < 1 and m > 24) having specific catalytic properties, made possible the development of new processes and catalysts for processing of hydrocarbon raw materials wide fractional composition (from hydrocarbon, C2to C10and above) and oxygen-containing organic compounds into high-octane gasoline or aromatic hydrocarbons at one stage.

Known methods of processing hydrocarbon, C2-CNow zeolites ZSM-5 and ZSM-11 General formula nNa2OAl2O3/mSiO2(where n < 1 and m > 24), including modified elements II, III, IV, V and VIII groups, for example, [U.S. Patent N 3953366, CL 01 J 29/06, 1976; N 4590323, class C 07 C 2/00, 1986; N 4861933, class C 07 C 2/52, 1989; Application CIS countries N 0355213, class B 01 J 29/00 C 07 C 15/00, 1990]. In General, the transformation of raw materials is possible in the temperature range of the reaction 200-815oC, pressures of 0.1 to 7 MPa, and the weight rate of feed of 0.05-400 h-1.

Known methods of increasing the octane number of the secondary gasoline of various processes to recycle hydrocarbon fraction, wikipaedia within 24-218oWith [U.S. Pat. USA N 3855115, class C 10 G 35/06, C 07 C 5/22, 1974; Application CIS countries N 0235416, class C 10 G 35/095, 1987]. According to the methods of the transformation of hydrocarbons, is performed on the catalysts containing zeolites of type ZSM-5,-11,-12,-23,-35,-48, including printed items II, III, and VIII groups, at temperatures of 260 815oC, pressures up to 3.5 MPa and the weight of the feed rate of the raw material is 0.1-20 h-1.

To improve properties of zeolite catalysts used zeolites modified with crystal frame obtained during the synthesis of the zeolite by complete or partial isomorphous substitution of aluminum atoms in alumbramiento zeolite framework atoms other e is the empirical formula aMen/2Cr2O3mSiO2(where Me is an alkali metal, and m > 20), prepare catalysts for the processes of cracking, hydrocracking, dewaxing, reforming, oligomerization, alkylation, isomerization of xylenes [U.S. Pat. France N 2463746, class C 01 B 33/20; B 01 J 23/86; C 07 C 11/00; C 10 G 11/04, 35/06, 49/04, 1980; U.S. Patent N 4299808, class C 01 B 22/20, 1981; N 4354924, class C 10 G 11/05, 1982] applied in the environment of the hydrogen-containing gas and hydrogen-free environment. For catalysts for conversion of hydrocarbons offered crystalline silicate (zeolite) of General formula nM2OY2O3XO2where Y is one or more elements selected from among Al, Fe, Cr, Y, Mo, As, Sb, Mn, Ga, B; X is Si or Ge; M is a monovalent metal cation; n and m are the corresponding coefficients [UK Application N 2193490, class C 01 B 33/28, 1988].

A method of refining olefins in gasoline and diesel fractions using isomerisation zeolite [U.S. Pat. USA, N 4861934, class C 07 C 2/02, 1985] . According to this method, the processing of olefins, C2-C8carried out at a temperature 175-375oC, a pressure of 1-20 MPa and velocity of 0.1-10 h-1the catalyst containing crystalline iron silicate with the structure of zeolite ZSM-5.

A method of obtaining high-octane d is this way the conversion of hydrocarbons is carried out at a pressure of 0.5 MPa, the temperature 350-650oC and space velocity of the gaseous raw material 100-10000 h-1the catalyst containing partially isomorphously zeolite General formula aMbAl2O3Ga2cSiO2where M is alkali or alkaline earth metal; a, b, c are the corresponding coefficients. You can use this zeolite exchanged with or coated with cations of different metals.

A method of obtaining gasoline fractions [U.S. Pat. RF N 1325892, class C 10 G 11/05, B 01 J 29/30, 1993]. According to this method, gasoline fractions, including those containing aromatic hydrocarbons, obtained by contacting a hydrocarbon feedstock at a temperature of 360-460oC, a pressure of 0.2 to 4 MPa and space velocity of the feedstock with zeolite catalyst. As the zeolite used aluminosilicate, whose skeleton is modified by the elements II, III, V, VI and VIII groups of the periodic system of General formula where enOm- one or two oxide elements II, III, V, VI and VIII groups, optionally, the catalyst may contain from 0.05 to 0.5 wt.% Pd.

Major General disadvantages of these methods are:

- relatively low outputs gasoline fractions;

- relatively low outputs aromatic in stanovova number of produced gasoline;

- use of high temperature reactions:

- processing of a narrow range of raw materials (only hydrocarbons).

Known combined methods of obtaining high-octane gasoline fractions from hydrocarbon material, combining the processing of individual fractions of raw materials or intermediate products on the catalysts containing isomorphously, including modified by various elements, zeolites ZSM-5 and ZSM-11, with the processes of separation (separation by distillation of raw material or intermediate products Patents of the Russian Federation N 2024585, class C 10 G 51/04, 1994: N 2034902, class C 10 G 35/095, 1995; N 2039790, class C 10 G 35/095, 1995; N 2050404, class C 10 G 35/095, 1995]. The main disadvantages of combined methods are the multi-stage process and processing the narrow range of raw materials (only hydrocarbons).

Optimizing the ratio of the components of the catalysts receive the latest to handle a wider range of raw materials in one stage. Thus, a method of obtaining aromatic hydrocarbons, C6-C10of hydrocarbons and/or alcohols (methanol) using isomorphically substituted zeolites [U.S. Pat. USSR N 936803, class C 07 C 15/02, 1982]. According to this method, the raw material containing hydrocarbon and/or methanol, at what Licata (zeolite). Used zeolite with structure of zeolite ZSM-5 contains in its frame (crystal lattice) isomorphously atoms of Fe and/or Fe and Al and has the General empirical formula (0,05-0,30)Na2OFe2O3(30-45)SiO2kH2O or (0,11-0,15)Na2OAl2O3(1,22-2,03)Fe2O3(71,1-90,9)SiO2kH2O, where k is the appropriate capacity factors. The main disadvantages of this method are:

- relatively low outputs gasoline fraction and/or aromatic hydrocarbons, and high outputs of gaseous reaction products of hydrocarbon, C1-C4due to high content of iron in the catalyst;

- relatively low-octane gasoline fractions obtained.

The closest in technical essence and the achieved effect is a method of producing high octane gasoline fractions and aromatic hydrocarbons, C8-C10of organic materials on the basis of hydrocarbons and/or oxygen-containing compounds [U.S. Pat. RF N 2069227, class C 10 G 35/04, 1996]. According to the selected prototype production of target products that perform special catalytic installation by contacting the feedstock with zeolite ka the project on gaseous and liquid fractions. Used catalyst contains zeolite ZSM-11 General empirical formula 0,04 Na2OAl2O3Fe2O352SiO2; or zeolite ZSM-5 General empirical formula of 0.03 Na2OAl2O30,3 Fe2O386SiO2modified 3 wt.% La or zeolite ZSM-5 General empirical formula of 0.02 Na2OAl2O30,3 Ga2O30,1 Fe2O386SiO2modified 0,1% Pd.

The main disadvantages of the prototype are:

- the use of relatively high temperature reaction (320-650oC), which leads to increased energy consumption for production.

- the relatively low yields of the target products;

- relatively low-octane gasoline fractions obtained.

The problem solved by the invention is to provide a method for producing high-octane gasoline fraction and/or aromatic hydrocarbons, C6-C10of hydrocarbon, C2-C12and/or oxygen-containing organic compounds, allowing to produce target products with higher yields and/or octane number of the gasoline fractions at lower temperatures of reaction.

This object is achieved in that the wysowa C2-C12and/or oxygen-containing organic compounds (alcohols, esters, and so on ) by contacting the feedstock at a temperature of 280 - 460oC (better 320-440oC) and a pressure of 0.1-4.0 MPa (preferably 0.5 to 2 MPa) with a catalyst containing a zeolite with structure of ZSM-5 or ZSM-11 General empirical formula (0,02-0,09)Na2OAl2O3(0,01-1,13)Fe2O3(27-212)SiO2kH2O modified the elements or compounds of elements of V, VI, VII and VIII groups in the amount of 0.05-5.0 wt.% or zeolite General empirical formula where enABOUTm- one or two oxide elements II, VI and VIII groups, a k - appropriate capacity factor, or zeolite General empirical formula where enOm- one or two oxide elements II, III, V and VI groups, and k is the corresponding capacity factor, modified by the elements or compounds of elements I, II, IV, V, VI, VII and VIII groups in the amount of 0.05-5.0 wt.%, with the subsequent separation of the products contacting gaseous and liquid fractions. Possible the implementation stage contacting of the feedstock with the catalyst in the presence of hydrogen-containing gas.

The catalysts are prepared by the known methods, varying in a ratio of boot components.

Based>/BR>- ability to carry out the stage of contacting the feedstock with a catalyst in the presence of hydrogen-containing gas.

The main advantages of the proposed method are:

- the possibility of obtaining the target product at lower temperatures the reaction;

- the possibility of obtaining gasoline with large outputs and/or octane number of gasoline and lower leg.

The effect is connected with optimization of the composition of the active sites of the zeolite catalyst obtained by a certain ratio of its components. The composition of the crystal lattice of the zeolite provides such a concentration and strength of acid sites, leading to the synthesis reaction and conversion of hydrocarbons, which might result in the implementation of deep transformation of raw materials at lower process temperatures. Modification of the catalyst are some items I, II, III, IV, V, VI, VII and VIII leads to additional formation of active centers, resulting in increased activity of the catalyst. In addition, the modification of the zeolite and the catalyst for some metals I, II, III, IV, V, VI, VII and VIII additionally allows you to process raw materials in the presence of wodorosoda regenerating period of operation of the catalyst and of life.

The essence of the proposed method and its practical applicability is illustrated by the following examples. Examples 1-2 - prototype examples 3-4 are similar to the prototype and is provided for comparison with the proposed method under comparable conditions, examples 5-19 - the proposed method.

Examples 1-2 prototype. Straight-run gasoline fraction (35-140oC) gas condensate, and having an octane number (PTS) - 67MM, is subjected to contacting with a zeolite-containing catalyst No. 1 at the reaction temperature T, pressure P and volume rate of flow of the liquid raw material . Products contact share with the release of hydrocarbon gases, gasoline fractions 35-205oC and fraction > 205oC. the Composition of the catalyst are given in table. 1, the process conditions, the yields of products, compositions and the octane number of the gasoline obtained are given in table. 2.

Example 3. Similar to example 1. As raw materials use a fraction of the hydrocarbon, C6-C8containing, wt.%: n - hexane - 30, isooctane - 30, cyclohexane - 30, toluene - 10 and has the estimated octane number (OCHp) - 71 MM. The composition of the catalyst N 2 are given in table. 1, the process conditions, the yields of products, the composition of the gasoline fraction and the estimated octane number lead is, terasul 25 wt.% n-pentane and 75% n-hexane and having the estimated octane number (OCHp) - 35 MM. The composition of the catalyst N 3 are given in table. 1, the process conditions, the yields of products, the composition of the gasoline fraction and the estimated octane number given in the table. 2.

Examples 5-19 illustrate the essence of the proposed method.

Examples 5-6. The fraction of hydrocarbons, C6-C8containing, wt.%: n-hexane - 30, isooctane - 30, cyclohexane - 30, toluene - 10 and has the estimated octane number (OCHp) - 71 MM, is subjected to contacting with the reaction temperature T, pressure P and volume rate of flow of the liquid feedstock with catalyst # 4. Products contact share with the release of hydrocarbon gases, gasoline fractions 35-205oC containing aromatic hydrocarbon, C6-C10and the faction > 205oC. the Composition of the catalyst are given in table. 1, the process conditions, the yields of products, the composition of gasoline fractions and their estimated octane number given in the table. 2.

Examples 7-8. Similar to example 5. As raw materials use of pentane-hexane fraction containing 25 wt.% n-pentane and 75% n-hexane and having OCHp= 35 MM. The composition of the catalyst No. 5 shown in table. 1, the process conditions, the outputs of the Roux 5. As raw materials use a fraction of the hydrocarbon, C6-C8containing, wt.%: n-octane - 30, isooctane - 30, cyclohexane - 30, toluene - 10 and has the estimated octane number (OCHp) - 56 MM. The compositions of the catalysts (NN 6, 7, 8 and 9, respectively) are given in table. 1; the process conditions, the yields of products, the composition and OCHpgasoline fractions are given in table. 2.

Examples 13-14. Similar to example 5. As raw materials use of hydrocarbon fraction with PTS= 64 MM, having the following size distribution,oC: N. K. - 36; about 10.% - 65, 50% - 107, 90% - 152, K. K. - 191 and containing hydrocarbons, wt. %: C2- 0,1; C3TO 0.6: C4- 1,7, C5- 5,5; C6- 14,3; C7- 28,7; C8- 28,9; C9AND 15.3; C10+of 4.9. The compositions of the catalysts (No. 10 and No. 11, respectively) are given in table. 1; terms of process, outputs, products, compositions and PTS gasoline fractions are given in table. 2.

Example 15. Hydrocarbon fraction C6-C8containing, wt.%: n-octane - 30, isooctane - 30, cyclohexane - 30, -10 toluene and having a calculated octane number (OCHabout) - 56 MM is subjected to contacting with the catalyst N 12 at the reaction temperature T = 460oC, pressure P = 0.5 MPa and space velocity of the liquid raw material = 4,0 h-1in the environment of hydrogen is of aktov, 3% fraction > 205oC and 65% gasoline fraction 35-205oC, containing 43% aromatic hydrocarbons, C6-C10and having OCHp= 91 MM. The yield of aromatic hydrocarbon, C6-C10- by 36.4%. The composition of the catalyst are given in table. 1.

Example 16. Propylene is subjected to contacting with the catalyst N 13 at the reaction temperature T = 350oC, pressure P = 0.1 MPa and space velocity of the gaseous raw material v= 1050 h-1(the composition of the catalyst are given in table. 1). Products contact share with allocation of 31 wt.% hydrocarbon gases, 67% of the gasoline fraction 35-205oC and 2% fraction > 205oC. Gasoline fraction containing 4% n-paraffins, 27% isoparaffins and naphthenes, 66% of aromatic and 3% olefinic hydrocarbons and has a PTSp= 88 MM. The yield of aromatic hydrocarbon, C6-C10- 44,2%.

Example 17. Propylene is subjected to contacting with the catalyst N 13 at the reaction temperature T = 280oC, pressure P = 0.5 MPa and the weight of the feed rate of the raw material g = 2,0 h-1(the composition of the catalyst are given in table. 1). Products contact share with allocation of 9 wt.% hydrocarbon gases, 68% of the gasoline fraction 35-205oC and 23% fraction > 205oC. Gasoline fraction has a PTSoC, P = 1.0 MPa and = 2,0 h-1with catalyst No. 14 (the composition of the catalyst are given in table. 1). Products contact share with the release of 5.4 wt.% water, 44.9% of hydrocarbon gas, 48.2% of gasoline fraction 35-205oC (including aromatic hydrocarbons, C6-C10- 21,7%) and 1.5% fraction > 205oC. the Outputs of the hydrocarbon reaction products in the hydrocarbon part is composed of, by weight. %: hydrocarbon gases is 47.5; gasoline fraction 35-205oC - 50,9 (including aromatic hydrocarbons, C6-C10- 22,9) and fraction > 205oC - 1,6. A gasoline fraction containing 30% of n-paraffins, 22% isoparaffins and naphthenes, 45% of aromatic and 3% olefinic hydrocarbons and has a PTSp= 74 MM.

Example 19. The mixture of oxygen-containing compounds containing 70 wt.% methanol and 30% dimethyl ether, subjected to contact at T = 360oC, P = 0.5 MPa and = 2,0 h-1with catalyst No. 14 (the composition of the catalyst are given in table. 1). Products contact share allocation to 39.9 wt.% water, 20,3% hydrocarbon gas, 38.7 percent gasoline fraction 35-205oC (including aromatic hydrocarbons, C6-C10- 25,2%) and 1.1% fraction > 205oC. the Outputs of the hydrocarbon reaction products in the hydrocarbon part of the amount, wt.%: coal is - 41,9) and fraction > 205oC - 1,8. A gasoline fraction containing 4% n-paraffins, 28% isoparaffins and naphthenes, 65% of aromatic and 3% olefinic hydrocarbons and has a PTSp= 88 MM.

Thus, from these examples it follows that compared to the prototype of the proposed method from a variety of hydrocarbons and/or oxygen-containing compounds to obtain a gasoline fraction and aromatic hydrocarbons, C6-C10with similar outputs and/or higher octane numbers at lower temperatures the reaction, and at equal temperatures the reaction is to obtain a gasoline fraction with large octane numbers and large outputs of aromatic hydrocarbons. Thus, from the comparison of examples of the prototype and the proposed method, when processing the same raw materials for the proposed method it is possible to get at lower temperatures the reaction - gasoline fraction and aromatic hydrocarbons, C6-C10with similar outputs and/or higher octane numbers (see examples NN 3 and 5, 4 and 7). When compared with the prototype of the temperature response of the proposed method it is possible to obtain a gasoline fraction with large octane numbers (see examples B>-C10- with large outputs (see examples NN 3 and 6, 4 and 8).

1. Method of producing high octane gasoline fractions and/or aromatic hydrocarbons, C6-C10of hydrocarbons and/or oxygen-containing compounds by contacting at elevated temperatures and pressures of 0.1 - 4 MPa with a catalyst containing a zeolite with structure of ZSM-5 or ZSM-11, in the crystal lattice which consists of atoms of aluminum and iron, with subsequent separation of the products contacting gaseous and liquid fractions, characterized in that stage contacting is performed with a catalyst containing zeolite General empirical formula (0,02 - 0,09)Na2O Al2O3(0,01 - 1,13)Fe2O3(27 - 212)SiO2kH2O modified the elements or compounds of elements of V, VI, VII and VIII groups in the amount of 0.05 - 5.0 wt.%, or zeolite General empirical formula where enABOUTm- one or two oxide elements II, VI and VIII groups, and k is the corresponding capacity factor, or zeolite General empirical formula where enOm- one or two oxide elements II, III, V and VI groups, and k is the corresponding capacity factor, modified by the elements or compounds of elements I, II, Ture 280 - 460oC.

2. The method according to p. 1, characterized in that the contacting of the feedstock with the catalyst is carried out in the presence of hydrogen-containing gas.

 

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