Method of producing high octane gasoline fractions and aromatic hydrocarbons (options)

 

Usage: petrochemistry. The inventive high-octane gasoline fraction and/or aromatic hydrocarbons With6-C10receive by successive contact of the flow of raw materials containing the arena, and/or naphthenes, and/or olefins and/or paraffins, wikipaedia 250oWith, and/or oxygen-containing organic compounds at elevated temperature and pressure, possibly in the presence of hydrogen, of regenerated catalyst are at least two different reaction zones respectively of the two reactors or in a single reactor unit with a supply or dissipation intermediate reaction flow between zones. The reaction products are cooled and separated by separation and rectification emitting fractions of hydrocarbon gases, gasoline fractions and/or aromatic hydrocarbons and fractions, wikipeida above 180-215oC. Implementation of the method is possible in two basic variants. According to the first temperature of the flow at the entrance to each subsequent downstream feed reaction zone at 5-50oC lower than the temperature of the flow at the entrance to each previous reaction zone and/or the reaction temperature in each subsequent along the feed to the reaction zone is ciruit initially with catalyst, with the concentration of proton centers or groups not below 40-50 Ámol/g with power on the scale of the proton affinity (RA) is not more than 1,200 kJ/mol, and then with a catalyst having a concentration of proton centers or groups not below 40-50 Ámol/g with RA not less than 1200 kJ/mol. Stage contacting is carried out at a temperature 300-480oC, a pressure of 0.1 to 6.0 MPa and a mass flow rate of feed of 0.3-10 h-1and regeneration of the catalyst is carried out at a temperature of 350-550oC and a pressure of 0.1 to 6.0 MPa initially regenerating gas with an oxygen content of 0.1 to 5.0 vol.%, and then with the oxygen content of 10-21%. Used the catalyst containing the silicate composition (0,02-0,32)Na2OAl2O3(0,003-2,4)EnOm(28-212)SiO2whereEnAboutm- one or two oxide elements II, III, V, VI and VIII groups of the Periodic system or zeolite type pentasil with the structure of ZSM-5 or ZSM-11 having the composition described by the General empirical formula (0,02-0,32)Na2OE2O3(28-212)SiO2kH2O, where e is at least one element can be modified at least one element and/or the connection element I-VIII groups in an amount of 0.01-10.0 wt.%. Effect: producing high-octane gasoline fractions with a low content of benzene and/or aromatic hydrocarbons With6-C10and expanding the range of recyclable materials. 2 S. and 6 C.p. f-crystals, 1 table.

The invention relates to methods of producing unleaded high-octane gasoline fractions with reduced benzene content and/or aromatic hydrocarbons With6-C10of hydrocarbons and/or oxygen-containing organic compounds.

Currently, high-octane unleaded 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.], and in General the technology of obtaining trademark high-octane unleaded gasoline is quite complex. Modern standards limit the content of aromatic hydrocarbons and/or benzene in motor gasoline, for example, the Russian standard GOST R 51105-97 limit the benzene content in gasoline 5,0% vol.

cities is a catalytic reforming process, carried out by means of platinum or polymetallic catalysts [Gureyev, A. A., Zhorov Y. M., Smidovich E. C. Production of high-octane gasoline. - M.: Chemistry, 1981, - 224 C.]. As raw materials of the process used previously hydrotreated hydrocarbon fraction, wikipaedia 200oC. the Major shortcomings of the reformer: - the sensitivity of the catalyst to the nature of the raw material is the preferred raw material reforming unit are hydrocarbon fractions 85-180oWith naphthenic base and in the processing of raw materials with high content of paraffin hydrocarbons is almost impossible to produce gasoline with PTS >82 MM; - high sensitivity of the catalyst to sulfur content in the raw materials required depth preliminary Hydrotreating raw materials; - the relatively high reaction temperature (480-550oC), which increases the energy consumption for production; - high benzene content in the produced reformate (7-15%), which limits the possibility of their use as a gasoline according to GOST R 51105-97 without further fractionation or processing; narrow range of recycled raw materials - processing only paraffin-naphthenic fractions, wikipaedia 200oC.

To reduce the benzene content in the and reforming, to remove the precursors of benzene; - fractionation of the resulting reformate to identify fractions containing benzene, with subsequent hydrogenation of benzene and the isomerization of the formed compounds (for example, the process RePEc) or with subsequent alkylation of benzene by contact with registertask fractions (for example, the process Alkymax).

A common shortcoming of these approaches obtain gasoline with a low content of benzene is a multi-stage, additional fractionation and combination of the various processes that lead to the appreciation of the whole process.

Thanks to the creation of the family of zeolites of type pentasil with the structure of ZSM-5, ZSM-11, having a specific molecular sieve and catalyst properties, the opportunity to develop new processes and catalysts for processing of hydrocarbon raw materials wide fractional composition (from hydrocarbons With2to C10and above) and oxygen-containing organic compounds into high-octane gasoline or aromatic hydrocarbons at one stage. To improve properties of zeolite catalysts used zeolites modified with crystal is uminia in alumbramiento zeolite framework atoms of other elements.

Known methods for processing hydrocarbons With2-C10in high-octane gasolines and their components (aromatic hydrocarbons) with the use of catalysts based on zeolite ZSM-5, ZSM-11 General empirical formula nNa2OAl2O3mSiO2(where n<1 and m>24), including modified elements II, III, IV, V and VIII groups (for example, [U.S. Patent 3953366, 01 J 29/06, 1976; 4590323, C 07 C 2/00, 1986; 4861933, C 07 C 2/52, 1989; European patent 0355213, 01 J 29/00, C 07 C 15/00, 1990; 0964903, With 10 G 35/095, 1998]). In General, the transformation of raw materials is possible in the range of the reaction temperature 200-815oWith pressure of 0.1 to 7.0 MPa, and the weight rate of flow of the liquid raw material is 0.05-400 h-1as in the environment of the hydrogen-containing gas and hydrogen-free environment.

Also known is a method of obtaining high-octane additives to gasoline, including aromatic hydrocarbons6-C10[Pat. USA 4554396, C 07 C 2/02, 1985]. According to this method, the conversion of hydrocarbons is carried out at a pressure of 0.5 MPa, a temperature of 350-650oC and space velocity of the gaseous raw material 100-10000 h-1the catalyst containing partially isomorphously zeolite General formula ambl2onselling metal; a, b, C, - the corresponding coefficients. You can use this zeolite exchanged with or coated with cations of different metals.

Major General shortcomings of the above described methods are: - the processing of a narrow range of raw materials (only hydrocarbons);
- the use of high reaction temperatures;
- relatively high outputs gaseous products;
- high benzene content in the resulting gasoline fractions.

The closest in technical essence and the achieved effect is a method of obtaining gasoline fractions of hydrocarbons [U.S. Pat. RF 1325892, With 10 G 11/05, 01 J 29/30, publ. 1993, bull. 41-42]. According to the selected prototype high-octane gasoline fractions, including aromatic hydrocarbons With6-C9produced by contacting a hydrocarbon feedstock at elevated temperature and pressure aluminosilicate catalyst composition (0,02-0,32)Na2OAl2O3(0,003-2,4)EnOm(28-212)SiO2,
whereEnAboutm- one or two oxide elements II, III, V, VI, VIII groups of the Periodic system, including modigene benzene in the resulting gasoline fractions and processing of a narrow range of raw materials - only hydrocarbons.

Object of the invention is to provide a method for producing high octane gasoline fractions with a low content of benzene and/or aromatic hydrocarbons With6-C10and expanding the range of recyclable materials.

The problem is solved in two main variants of the method:
- high-octane gasoline fraction and/or aromatic hydrocarbons With6-C10receive from wikipaedia 250oWith hydrocarbon containing arena and/or naphthenic and/or olefins and/or paraffins, and/or oxygen-containing organic compounds by contacting the stream of feedstock at elevated temperature and pressure with a catalyst containing a crystalline silicate composition (0,02-0,32)Na2OAl2O3(0,003-2,4)EnOm(28-212)SiO2,
whereEnOm- one or two oxide elements II, III, V, VI and VIII groups of the Periodic system, or zeolite type pentasil with the structure of ZSM-5 or ZSM-11 having the composition described by the General empirical formula (0,02-0,32)Na2OE2O3Al2O3(0,003-2,4)EnOm(28-212)SiO2,
whereEnOm- one or two oxide elements II, III, V, VI and VIII groups of the Periodic system, or zeolite type pentasil with the structure of ZSM-5 or ZSM-11 having the composition described by the General empirical formula (0,02-0,32)Na2OE2O3(28-212)SiO2kH2Oh, where e is at least one element of a number of Al, Ga, In, Fe, a k is the corresponding coefficient of capacity, while stage contacting of the feedstock with the catalyst is carried out sequentially in at least two reaction zones in a single reactor device or at least two reactors, with a supply or dissipation intermediate reaction flow between zones, initially with a catalyst, with the concentration of proton centers or groups not below 40-5 is the acidity of the proton centers or groups not below 40-50 Ámol/g with RA not less than 1200 kJ/mol, subsequent cooling, condensation, separation and distillation products contact in the respective process apparatuses emitting fractions of hydrocarbon gases, fractions, wikipeida above 185-215oWith the gasoline fraction and/or aromatic hydrocarbons, at this stage of the oxidative regeneration of the catalyst is carried out at elevated temperature initially regenerating gas with low oxygen content, and then with a higher concentration of oxygen.

According to the second variant of the method is possible that the temperature of the flow at the entrance to each subsequent downstream feed reaction zone was 5-50oC lower than the temperature of the flow at the entrance to each previous reaction zone and/or the reaction temperature in each subsequent along the feed to the reaction zone was 5-50oC lower than the reaction temperature in each of the preceding reaction zone.

For both options you can use catalyst, where the silicate or zeolite, and/or the catalyst modified or contains at least one element and/or the connection element 1-VIII groups in an amount of 0.01-10.0 wt.%
For both variants of the method stage contacting of the feedstock with the catalyst is carried out at the pace of the Torah is carried out at a temperature of 350-550oC and a pressure of 0.1 to 6.0 MPa initially regenerating gas with an oxygen content of 0.1 to 5.0 vol.%, and then with the oxygen content of 10-21%. It is possible during the processing of raw materials to increase the reaction temperature in each reaction zone at an average speed of 0.1 to 3o/h Possible the implementation stage contacting of the feedstock with the catalyst in the presence of hydrogen-containing gas at a hydrogen/hydrocarbon 0,1-10,0.

The catalysts are prepared by the known methods, varying in a ratio of boot components. At the stage of preparation of the active forms of the zeolites used are known modification methods (decationization, dealumination, ionic and cationic exchange, impregnation, heat treatment, etc. in various combinations.

The main distinctive features of the proposed method are:
- processing of raw materials to the stage of its contact with the catalyst in at least two reaction zones in a single reactor device or at least two reactors, with a supply or dissipation intermediate reaction flow between zones when the temperature of the flow at the entrance to each subsequent downstream feed reaction zone at 5-50oC lower than the temperature of the feed to the reaction zone at 5-50oC lower than the reaction temperature in each of the previous reaction zone;
- processing of raw materials to the stage of contact initially with the catalyst having a concentration of proton centers or groups not below 40-50 Ámol/g with a force in the scale of the proton affinity (RA) is not more than 1,200 kJ/mol, and then with a catalyst having a concentration of proton centers or groups not below 40-50 Ámol/g with RA not less than 1200 kJ/mol;
- possibility of processing at the stage of contact initially with the catalyst having a concentration of proton centers or groups not below 40-50 Ámol/g with a force in the scale of the proton affinity (RA) is not more than 1,200 kJ/mol, and then with a catalyst having a concentration of proton centers or groups not below 40-50 Ámol/g with RA not less than 1200 kJ/mol when the temperature of the flow at the entrance to each subsequent downstream feed reaction zone at 5-50oC lower than the temperature of the flow at the entrance to each previous reaction zone and/or the reaction temperature in each subsequent along the feed to the reaction zone at 5-50oC lower than the reaction temperature in each of the previous reaction zone;
- possibility of use in the catalyst of the zeolite type pentasil with the structure of ZSM-5 or ZSMb>O3(28-212)SiO2kH2Oh, where e is at least one element of a number of Al, Ga, In, Fe, a k is the corresponding coefficient of moisture content;
- the possibility of using different catalyst composition, where the silicate or zeolite, and/or the catalyst modified or contains at least one element and/or the connection element I-VIII groups in an amount of 0.01-10.0 wt.%;
- cooling, condensation, separation and rectification products contact in the respective process apparatuses emitting fractions of hydrocarbon gases, fractions, wikipeida above 185-215oWith the gasoline fraction and/or aromatic hydrocarbons;
- implementation stage of contacting raw material under specified conditions and stage of oxidative regeneration of the catalyst at elevated temperature initially regenerating gas with low oxygen content, and then with greater oxygen concentration at specified parameters;
- possibility of processing at the stage of its contact with the catalyst to increase the reaction temperature in each reaction zone at an average speed of 0.1 to 3o/h;
- possibility of processing at the stage of its kontaktirovaete process can be a hydrocarbon, C2-C12and their fractions, wikipaedia 250oWith, and/or oxygen-containing organic compounds (alcohols, esters, and so on), and/or mixtures thereof.

Achieved results associated with sequential processing of raw materials in the different reaction zones, differing mainly chemical reactions as a source of components, raw materials and intermediate products of its transformation, in particular in the first phase reactions of cracking and aromatization leading to the formation of shorter paraffins and aromatic hydrocarbons (including benzene), and in the second stage reactions alkylation intermediate olefins, aromatic hydrocarbons (including benzene) to form alkylaromatic compounds and reactions parallelomania aromatic hydrocarbons. The concentration of benzene in the reaction products is dramatically reduced.

It is known that catalysts of acid-base type, including the zeolites of type pentasil, when the conversion of hydrocarbons occur:
a) primary reactions of rupture of C-C linkages with the formation of olefin and paraffin fragments:
R1-CH2-CH2-CH2-R2__R1-CH=CH2+H3C-R2

C) the reaction of alkylation of benzene with olefins education alkylaromatic hydrocarbons:

g) reaction of isomerization, disproportionation, dealkylation of the resulting aromatic hydrocarbons, including reaction transaminirovania (parallelomania):

Through the stage of formation of olefinic fragments occurs the conversion of oxygen-containing organic compounds (alcohols, ethers) in paraffin and aromatic hydrocarbons.

The changing conditions of chemical reactions it is possible to influence the selectivity of the formation of certain hydrocarbons. Thus, the temperature increase of the process leads to increased reaction rates, cracking and aromatization leading to the increase of the content of gaseous products and aromatic hydrocarbons, as well as shifts thermodynamic equilibrium in the direction of the reactions dealkylation and disproportionation, resulting in increasing the content of benzene in the aromatic component of the reaction products and, accordingly, in the gasoline fraction. The change in strength and concentration of the proton centres (Oh-groups) zeolite catalyst takeany reactions of cracking of C-C linkages and flavoring, weaker proton centers are not active in the reactions of breaking C-C bonds, but are involved in the reactions of alkylation and transaminirovania aromatic compounds, which leads to a decrease in the content of benzene in the reaction products.

thermal mode of operation of the catalyst at which the temperature of the flow at the entrance to each subsequent downstream feed reaction zone at 5-50oC lower than the temperature of the flow at the entrance to each previous reaction zone, and/or the reaction temperature in each subsequent along the feed to the reaction zone at 5-50oC lower than the reaction temperature in each of the preceding reaction zone, contributes to the flow in the first zone of the reactions of cracking and aromatization, and in the second zone - alkylation reactions and transaminirovania that leads to the reduction of benzene content by becoming a alkylaromatic hydrocarbons.

Optimization of the composition of the crystal lattice of the zeolite and the implementation of the uniform distribution it is isomorphic replacement of elements leads to the formation of acid sites with power and concentration, necessary for the occurrence of specific target reactions. The modification of the silicate or zeolite, and the Yu active centers of acid-base action of different forces, resulting in increased activity and selectivity of the catalyst for certain reactions. So, loaded into the first catalytic zone of the catalyst with acid strength centers on a scale RA (affinity proton) is not higher than 1,200 kJ/mol and the concentration of proton centers or groups not below 40-50 Ámol/g is high activity in the reaction of cleavage of C-C bonds in paraffin and naphthenic constituents of the raw material with the formation of olefins, paraffins and aromatic hydrocarbons, and loaded the second zone of the catalyst with RA not below 1200 kJ/mol less active in aromatization reactions, but catalyzes the reaction of alkylation and transaminirovania, which leads to a decrease in the content of benzene due to its transformation into alkylaromatic hydrocarbons.

In addition, the modification of the silicate or zeolite, and/or catalyst some items I-VIII groups and/or their compounds can increase the duration mezhregionalnogo mileage catalyst and life. The modification of the silicate or zeolite, and/or catalyst for some metals I-VIII groups and/or their compounds allows you to extend the range of recycled raw materials, and also allows you to process raw materials in prichina duration mezhregionalnogo period of operation of the catalyst.

During the processing of raw materials on the catalyst processes coke formation, leading to reversible deactivation of the catalyst, resulting in a lower level of activity. To maintain the level of activity and increase the duration mezhregionalnogo mileage catalyst in the processing of raw materials, the reaction temperature in each reaction zone increases with a certain speed. To restore the activity level of the catalyst periodically carry out its oxidative regeneration, which consists in burning the formed coke on the catalyst oxygen-containing gas is initially low, and then with a high content of oxygen.

The modification of the silicate or zeolite, and/or catalyst for some metals I-VIII groups allows you to lower the temperature stage of regeneration, which increases the service life of the catalyst.

The method is as follows. Raw materials, possibly in a mixture with a hydrogen-containing gas is preheated to the reaction temperature in the corresponding process equipment (heat exchangers, furnaces, etc.,) and subjected to successive contacts of at least two or more reaction topramezone the reaction mixture with the catalyst) may be located on or in different reactors isothermal or adiabatic type or in a single reactor, multiple device (for example, in the reactor shelving type). As a result of leaking on the catalyst of chemical reactions with depending on the composition of raw materials exothermic or endothermic heat effect of the reaction temperature on catalyst layer in each reaction zone is changed, resulting in the flow of the reaction mixture after each reaction zone enters with a temperature different from the temperature of the flow at the entrance to this zone. For optimum working conditions of the catalyst intermediate, the reaction flow between the reaction zones, depending on thermal effect of the reaction is cooled (in the case of exothermic process) or heated (in the case of an endothermic process) in the corresponding process equipment (heat exchangers, furnaces, etc.,) to the reaction temperature during the subsequent feed of the reaction zone.

After the last on-the-go feed the reaction zone of the reaction products are cooled in the corresponding process equipment (heat exchangers, refrigerators, etc.,) and is divided into a number of gaseous and liquid fractions by separation and rectification in the relevant technological devices emitting fractions of hydrocarbon gases, high-octane gasoline or aromaticheskoe fraction can be used as a high-octane component of gasoline, raw materials for the processes of petrochemical synthesis, solvent-based aromatic hydrocarbons or may be subjected to fractionation for separation of individual aromatic hydrocarbons.

The reaction temperature is determined depending on the composition of the feedstock and the type of produce the target product (for example, production of gasoline-type AI-80, AI-95 or the production of aromatic fraction). To increase the duration mezhregionalnogo mileage catalyst, which depends on the type of raw materials and the reaction conditions, it is possible to increase the reaction temperature at an average speed of 0.1 to 3o/h in proportion to the degree of deactivation of the catalyst in such a way as to maintain the quality and group composition of the products at the same level.

The coke formation processes occurring in the zeolite-containing catalyst during the processing of hydrocarbons, lead to the reversible deactivation of the catalyst, resulting in a lower level of activity, and consequently, deterioration in the quality of gasoline (lower octane) and reduction of the yield of aromatic hydrocarbons. To restore the activity level of the catalyst periodically carry out his equilibrate, so separately.

Stage of catalyst regeneration is carried out at a temperature of 350-550oC and a pressure of 0.1 to 6.0 MPa initially regenerating gas with an oxygen content of 0.1 to 5.0 vol.% for isothermal reactors (tubular or shell and tube type) or of 0.1-2.0 vol.% for adiabatic and/or shelf reactors, and then 10-21%. Regenerating gas is produced by mixing air with nitrogen. You may receive the regenerating gas by mixing part of the exhaust gas regeneration supplied to the recirculation with air or with air and nitrogen.

The essence of the proposed method and its practical applicability is illustrated by the following examples. Example 1 - prototype examples 2-15 - the proposed method.

Example 1 - the prototype. The fraction of gas condensate NC-140oWith octane (PTS) 68 MM (motor method), containing 1.2 wt.% aromatic hydrocarbons, including 0.1% benzene, is subjected to contacting with the reaction temperature Tp= 420oC, pressure P=1.0 MPa and a space velocity of liquid raw materials= 2,0 h-1with a catalyst consisting of 70 wt.% crystalline aluminosilicate iron composition 0,04 Na2AboutAl2Aboutthis is formed 32.9 wt.% hydrocarbon gases and 67,1% gasoline fraction, containing 65.2% of aromatic hydrocarbons, including a 4.1% benzene.

Example 2. Straight-run gasoline fraction (32-144oC) oil, containing 4.5 wt. % of aromatic hydrocarbons, including 0.2% of benzene, heated and under a pressure of 1.0 MPa, a space velocity of liquid raw materials 2,0 h-1subjected to serial communication in two reaction zones with a zeolite-containing catalyst 2 (composition of the catalyst are presented in the table) in two sequential isothermal tubular reactors, the annular space which serves gaseous coolant. The reaction temperature in the first reactor is 340oWith, and in the second case 320oC. the Products of the probe is cooled and separated by separation and rectification in the relevant technological devices with the release of hydrocarbon gases, gasoline fraction NC-205oWith and fraction >205oC. the Yield of gasoline fraction makes 76.6 wt. % missed raw materials; it comprises 25% of aromatic hydrocarbons, including - 0,34% benzene.

Due to the processes of coke formation is reversible deactivation of the catalyst, leading to a decline in catalyst activity, as a result of ceracchi. Periodically to restore the initial level of activity of the catalyst is held oxidative regeneration, which consists in burning the formed coke on the catalyst oxygen-containing gas. Regenerating gas with oxygen content of 5% by vol. at a pressure of 0.15 MPa heated to a temperature of 370oWith and served successively through both reactor or in parallel in both reactor zakochany catalyst. In the exothermic reaction of the combustion of catalyst coke temperature in the combustion zone of coke 500oC. After burnout of the main part of the catalyst coke content of oxygen in the gas increases to 21%. and carry out the regeneration of the catalyst at 520oC.

Example 3. The fraction of hydrocarbons, C6-C8, wikipaedia in the temperature range 68-111oWith containing 30 wt.% n-paraffins, 30% isoparaffins, 30% naphthenes and 10% of aromatic hydrocarbons and having a calculated octane number (OCHp) - 71 MM, is subjected to contacting with the reaction temperature of 340oC, a pressure of 1.0 MPa and a space velocity of liquid raw materials 2,0 h-1with the catalysts 3 and 4, located respectively in the reaction zones 1 and 2 two isothermal Rea the ale proton affinity RA= 1180 kJ/mol, and the catalyst 4 has a proton centers with RA=1210-1250 kJ/mol and the total concentration of 92 Ámol/, the Compositions of the catalysts are given in table. Products contact share with the release of 29.1 wt.% gaseous products of 1.9% fraction, wikipeida above 205oWith, and 69.0% of the gasoline fraction 35-205oWith the estimated octane number of 95 MM. The content of aromatic hydrocarbons With6-C10in the gasoline fraction is 39.2%, including 0,71% benzene.

Regeneration of the catalyst is carried out analogously to example 2.

Example 4. Similar to example 3. As raw materials use of straight-run gasoline fraction, wikipaedia in the interval 24-144oWith and containing a 40.8 wt.% normal, 52,9% of isomerized and cyclic paraffins and 6.3% of aromatic hydrocarbons, including 0.55% benzene. The process is carried out at a reaction temperature of 360oC, a pressure of 1.5 MPa and a space velocity of liquid raw materials 4,0 h-1. Products contact share emitting 82,6% gasoline fraction 35-205oWith containing 28.9% of aromatic hydrocarbons With6-C10including 0,63% benzene. Regeneration of the catalyst is carried out analogously to example 2.

Example 5. Raw materials of example 4 at a pressure of 1.5 MPa prior the two adiabatic reactors. The temperature of the raw input flow in the first reactor is 370oC, the temperature of the reaction stream at the inlet to the second reactor is 345oWith mass feed rate of the liquid raw material to the total loading of catalyst in the first or second reactors - 2,1 h-1. After the 2nd reactor, the reaction products are cooled, condensed and separated in the respective processing units by separation with separation of hydrocarbon gases1-C4and rectification emitting hydrocarbon (including liquefied gases With3-C4and gasoline5+. The total yield of hydrocarbon gases With1-C4- 37,2 wt.%, gasoline fraction to 62.8%; the yield of aromatic hydrocarbons is 30.7%. Gasoline fraction contains 42,5% isoparaffins and naphthenes, 8.6% of n-paraffins and 48.9% of aromatic hydrocarbons With6-C10, including benzene - 0,96%, and by all indicators corresponds to gasoline AI-92.

After a decrease in the activity of the catalyst caused by the process of coke formation, which leads to a decrease in the yield of aromatic hydrocarbons and drop the octane number of the gasoline fraction obtained, carry out oxidative regeneration of the catalyst, lies with the oxygen content of 1.5% vol. at a pressure of 1.0 MPa heated to a temperature of 360oWith and served successively in both reactor zakochany catalyst. In the exothermic reaction of the combustion of catalyst coke temperature in the combustion zone of coke is 520oC. After burnout of the main part of the catalyst coke content of oxygen in the gas is increased to 15% vol. and carry out the regeneration of the catalyst at 520oC.

Example 6. As raw materials use of straight-run gasoline fraction NK-144oWith containing of 25.9 wt.% n-paraffins, 67.6% of isoparaffins and naphthenes and 6.5% aromatic hydrocarbons, including 2,33% benzene. Raw materials at a pressure of 1.0 MPa is preheated, evaporated and subjected to contacting a series of two adiabatic reactors, the first reactor loaded with catalyst 6, which has a concentration channel proton centers 146 Ámol/g with RA= 1180 kJ/mol; the temperature of the raw material input in the first reactor is 360oC. In the second reactor loaded with catalyst 7, having a proton centers with RA=1205-1210 kJ/mol, with a total concentration of 78 Ámol/g, the temperature of the reaction stream at the inlet to the second reactor is 340oC. the Volumetric rate of flow of the liquid raw material to the total loading of catalyst in the first-in the cool and share in the relevant technological devices emitting an increase of 22.7 wt.% hydrocarbon gases With1-C4and 77.3% gasoline fraction C5-215oC. Gasoline fraction contains 59,3% isoparaffins and naphthenes, 11.5% of n-paraffins and 29.2% of aromatic hydrocarbons With6-C10including 1.3% of benzene. The conversion of benzene was 43.6%. Regeneration of the catalysts is carried out analogously to example 5.

Example 7. Analogous to example 2. In is used as raw material mixture consisting of 76 wt.% n-hexane and 24% of 2-propanol. The raw material is heated, evaporated and subjected to contacting a series of two isothermal reactors at P= 1.0 MPa and=2,0 h-1with catalyst 8, the temperature in the first reactor is 380oWith the temperature in the second reactor 350oC. Products contact share in the relevant technological devices with the release of 6.2 wt. % water, 34.8% of hydrocarbon gas, 57.3% of gasoline fraction 35-205o(Including aromatic hydrocarbons6-C10- 23,9%) and 1.7% fraction >205oC. the Hydrocarbon reaction products contain, wt.%: hydrocarbon gases were 37.1; gasoline fraction 35-205oWith - 61,1 (including aromatic hydrocarbons6-C10- 25,5) and fraction >205oC - 1.8. Gasoline fraction comprises 23% of n-paraffins, 33,2% isoparaffins and naphthene wikipaedia in the temperature range 81-125oWith containing 30 wt.% n-paraffins, 30% isoparaffins, 30% naphthenes and 10% of aromatic hydrocarbons and having a calculated octane number (OCHp) 56 MM, is subjected to contacting with the catalyst 9 a series of two isothermal reactors at temperatures of 420 and 380oWith, respectively, the pressure P=1.0 MPa and a space velocity of liquid raw materials=3,0 h-1in the environment of hydrogen at a molar ratio of N2/SN=6. Products contact share with the allocation of 30 wt.% gaseous products, 2% fraction, wikipeida above 205oS, and 68% of the gasoline fraction 35-205oWith containing 45% of aromatic hydrocarbons With6-C10including benzene and 0.8%, and having a PTSp= 88 MM. The yield of aromatic hydrocarbons With6-C10- 30,6%. The composition of the catalyst shown in the table.

Regeneration of the catalyst is carried out analogously to example 2.

Example 9. The mixture of oxygen-containing compounds containing 70 wt.% methanol and 30% dimethyl ether is subjected to contacting in 4 sequential reaction zones shelf reactor with catalyst 10 (composition of the catalyst shown in the table). The flow temperature of the feedstock at the inlet of the reactor T=380oWith P=0.5 MPa andoWith and served in the following reaction zone; in the third and fourth zones of the reaction stream is served with temperatures 365 and 360oS, respectively. Products contact cooled and share in the relevant technological devices emitting and 39.9 wt.% water, 20,3% hydrocarbon gas, 38.7 percent gasoline fraction 35-205o(Including aromatic hydrocarbons6-C10- 25,2%) and 1.1% fraction >205oC. the Outputs of the hydrocarbon reaction products in the hydrocarbon part of the amount, wt.%: hydrocarbon gases to 33.8; gasoline fraction 35-205oWith - 64,4 (including aromatic hydrocarbons6-C10- 41,9); fraction >205oC - 1.8. Gasoline fraction contains 5.2% n-paraffins, 29.4% of isoparaffins and naphthenes, 1.3% of olefinic and 65,1% of aromatic hydrocarbons, including benzene was 1.9%, and has a PTSp=88 MM.

Regeneration of the catalyst is carried out analogously to example 5.

Example 10. Similar to example 5. Sirvani with catalyst 11 (composition shown in the table) in the reaction zones of the two adiabatic reactors. The temperature of the raw input flow in the first reactor 360oC, the temperature of the reaction stream at the inlet to the second reactor 340oWith mass feed rate of the liquid raw material to the total loading of catalyst in the first or second reactor for 1.5 h-1. After the 2nd reactor, the reaction products are cooled, condensed and separated by separation with separation of 26.4 wt.% hydrocarbon gases With1-C4and 73,6% gasoline fraction C5+(including aromatic hydrocarbons 30,5%). Gasoline fraction contains 52,4% isoparaffins and naphthenes, 6.1% of n-paraffins and 41.5% of aromatic hydrocarbons With6-C10, including benzene - 1,2%.

Example 11. Analogous to example 8. Raw materials of example 3 is subjected to successive contact with the catalyst 12 in two isothermal reactors at temperatures of 370 and 340oWith, respectively, the pressure P=0.5 MPa and a space velocity of liquid raw materials=2,0 h-1in the environment of hydrogen at a molar ratio of N2/SN=4. The composition of the catalyst, which contains ferrosilicate with the structure of ZSM-5 is shown in the table. Products contact share with allocation of 27 wt.% gaseous products, a 1% fraction, wikipeida above 205oS, and 72% of gasoline's and 30.5% of aromatic hydrocarbons With6-C10including benzene to 0.63%.

The composition of the catalyst shown in the table. Regeneration of the catalyst is carried out analogously to example 2.

Example 12. As a raw material, a mixture of hydrocarbons6-C8and alcohol, wikipaedia in the temperature range 63-125oWith and containing 23 wt.% n-octane, 24% of isooctane, 23% of cyclohexane, 10% hexene-1, 10% toluene and 10% 2-propanol. The raw material is preheated, evaporated and at a pressure of 1.0 MPa is subjected to sequential processing in two isothermal reactors. In the first reactor loaded with catalyst 6, which has a concentration channel proton centers 146 Ámol/g with RA=1180 kJ/mol; the temperature of the feedstock at the inlet to the first reactor 340oC. In the second reactor loaded with catalyst 10 with proton centers with RA=1205-1250 kJ/mol, with a total concentration of 85 Ámol/g; the temperature of the reaction stream at the inlet to the second reactor 310oC. the Volumetric rate of flow of the liquid raw material to the total loading of catalyst in the first or second reactors - 2,0 h-1. After the 2nd reactor, the reaction products are cooled and separated with separation of 3 wt.% the aqueous phase, 19% of hydrocarbon gases With1-C4, 76.7 percent gasoline fraction 35-205o(Including aromatic optoporation and naphthenes, less than 1% olefin, 38% of aromatic hydrocarbons, including benzene - 0,85%.

The compositions of the catalysts are given in table. Regeneration of the catalysts is carried out analogously to example 2.

Example 13. As raw materials use of hexene-1. The raw material is pre-heated and under a pressure of 1.0 MPa, the space velocity of the liquid raw material 1.9 h-1subjected to serial communication with catalyst 13 in two sequential isothermal tubular reactors, the annular space which serves cold coolant that ensures the removal of excess heat released during the transformation of raw materials on the catalyst in the tube space. The reaction temperature in the first reactor is 340oWith, and in the second case 320oC. the reaction Products are cooled and share with the release of 12.2 wt.% hydrocarbon gases With1-C4and 79,4 wt.% high-octane gasoline fraction With5-205oWith 8.4% diesel fraction >180oC. Gasoline fraction contains 20% of aromatic hydrocarbons, including 0.3% of benzene, and has an octane rating of 81 MM.

The catalyst composition containing the gallosilikata with the structure of zeolite ZSM-5, are presented in the table. Regeneration of catalysts spend an is ewout, evaporated and subjected to successive contact with the catalyst 14 (composition of the catalyst are presented in the table) in the reaction zones of the two adiabatic reactors. The temperature of the raw input flow in the first reactor is 360oC, the temperature of the reaction stream at the inlet to the second reactor is 340oC; mass feed rate of the liquid raw material to the total loading of catalyst in the first or second reactors - 3,1 h-1. After the 2nd reactor, the reaction products are cooled to 35oWith and share in debutanizer with the release of hydrocarbon gases With1-C4and liquid fractions With5+. The total yield of hydrocarbon gases With1-C4for 23.2 wt.%, gasoline fraction of 76.8%. Gasoline fraction contains 21.9% of aromatic hydrocarbons With6-C10, including benzene - 0.6%, and has an octane rating of 83 MM.

Example 15. Similar to example 6. As a raw material, a mixture of hydrocarbons With6-C8, wikipaedia in the temperature range 63-125oWith and containing cyclohexane, hexene-1, n-octane and isooctane in a ratio of 1:1:1:1 mass. The raw material is preheated, evaporated and at a pressure of 2.0 MPa is subjected to successive contact with the catalyst in two Oh centers 130 Ámol/g, characterized with RA=1180 kJ/mol, in the second reactor catalyst 15 with proton centers with RA=1205-1250 kJ/mol, with a total concentration of 62 Ámol/, the Temperature of the feedstock at the inlet to the first reactor 340oC, the temperature of the reaction stream at the inlet to the second reactor 330oWith; the volumetric rate of flow of the liquid raw material to the total loading of catalyst in the first or second reactor for 1.5 h-1. After the 2nd reactor, the reaction products are cooled and share with the release of 18.3 wt.% hydrocarbon gases With1-C4and 81.7 per cent of high-octane gasoline fraction With5+. Fraction With5+contains 36,7% of aromatic hydrocarbons With6-C10including 0.8% of benzene.

The compositions of the catalysts are given in table. Regeneration of the catalysts is carried out analogously to example 5.


Claims

1. Method of producing high octane gasoline fractions and/or aromatic hydrocarbons With6-C10from a hydrocarbon feedstock by contacting the stream of feedstock at elevated temperature and pressure with a catalyst, wherein the catalyst containing the silicate composition (0,02-0,32)PA2OAl2O3(0/img>EnOm- one or two oxide elements II, III, V, VI and VIII groups of the Periodic system or zeolite type pentasil with the structure of ZSM-5 or ZSM-11 having the composition described by the General empirical formula (0,02-0,32)PA2OE2O3(28-212)SiO2kN2O, where e is at least one element of a number of Al, Ga, In, Fe, a k is the corresponding coefficient of moisture content, use of hydrocarbon raw material containing the arena, and/or naphthenes, and/or olefins and/or paraffins, wikipaedia 250oWith, and/or oxygen-containing organic compounds, the stage of contacting the feedstock with a catalyst carried out sequentially in at least two reaction zones in a single reactor device or at least two reactors, with a supply or dissipation intermediate reaction flow between zones, and the temperature of the flow at the entrance to each subsequent downstream feed reaction zone at 5-50oC lower than the temperature of the flow at the entrance to each previous reaction zone and/or the reaction temperature in each subsequent along the feed to the reaction zone at 5-50oC lower than the reaction temperature in each of the previous somnologica devices emitting fractions of hydrocarbon gases, faction, wikipeida above 180-215oWith the gasoline fraction and/or aromatic hydrocarbons, at this stage of the oxidative regeneration of the catalyst is carried out at elevated temperature initially with a regenerating gas with low oxygen content, and then with a higher concentration of oxygen.

2. Method of producing high octane gasoline fractions and/or aromatic hydrocarbons With6-C10from a hydrocarbon feedstock by contacting the stream of feedstock at elevated temperature and pressure with a catalyst, wherein the catalyst containing the silicate composition (0,02-0,3 2)PA2OAl2O3(0,003-2,4)EnOm(28-212)SiO2whereEnAboutm- one or two oxide elements II, III, V, VI and VIII groups of the Periodic system or zeolite type pentasil with the structure of ZSM-5 or ZSM-11 having the composition described by the General empirical formula (0,02-0,32)PA2OE2O3(28-212)SiO2kH2O, where e is at least one element of a number of Al, Ga, In, Fe, a k - appropriate comparative, wikipaedia 250oWith, and/or oxygen-containing organic compounds, the stage of contacting the feedstock with a catalyst carried out sequentially in at least two reaction zones in a single reactor device or at least two reactors, with a supply or dissipation intermediate reaction flow between zones, initially with a catalyst having a concentration of proton centers or groups not below 40-50 Ámol/g with power on the scale of the proton affinity (RA) is not more than 1,200 kJ/mol, and then with a catalyst, with the concentration of proton centers or groups not below 40-50 Ámol/g with RA not less than 1200 kJ/mol, subsequent cooling, condensation, separation and distillation products contact in the respective process apparatuses emitting fractions of hydrocarbon gases, fractions, wikipeida above 180-215oWith the gasoline fraction and/or aromatic hydrocarbons, at this stage of the oxidative regeneration of the catalyst is carried out at elevated temperature initially with a regenerating gas with low oxygen content, and then with a higher concentration of oxygen.

3. The method according to PP.1 and 2, characterized in that the silicate or zeolite modified by mentalitywise fact, the catalyst modified or contains at least one element and/or the connection element I-VIII groups in an amount of 0.01-10.0 wt.%.

5. The method according to PP.2-4, characterized in that the temperature of the flow at the entrance to each subsequent downstream feed reaction zone at 5-50oC lower than the temperature of the flow at the entrance to each previous reaction zone and/or the reaction temperature at the entrance to each previous reaction zone in each subsequent downstream raw material reaction zone at 5-50oC lower than the reaction temperature in each of the preceding reaction zone.

6. The method according to PP.1-5, characterized in that stage contacting is carried out at a temperature 300-480oC, a pressure of 0.1 to 6.0 MPa and a mass flow rate of feed of 0.3-10 h-1and regeneration of the catalyst is carried out at a temperature of 350-550oC and a pressure of 0.1 to 6.0 MPa initially regenerating gas with an oxygen content of 0.1 to 5.0 vol.%, and then with oxygen 10-21% vol.

7. The method according to PP.1-6, characterized in that during the processing of raw materials, the reaction temperature in each reaction zone to increase at an average speed of 0.1 to 3oS/h

8. The method according to PP.1-7, characterized in that the stage of contacting the feedstock with the catalyst is carried out in prisutstvie the

 

Same patents:

The invention relates to the field of chemistry, and in particular to methods of obtaining aromatic hydrocarbons from light hydrocarbons, including petroleum gas terminal stages of separation
The invention relates to the synthesis of the catalysts used, in particular, for the conversion of hydrocarbons into high-level components of motor fuels, aromatic hydrocarbons

The invention relates to compositions that can be used for the conversion of hydrocarbons in the C6-C8aromatic hydrocarbon and the olefin, to a method for producing the composition and method of using the composition for the conversion of hydrocarbons in the C6-C8aromatic hydrocarbon and olefin
The invention relates to a method of processing hydrocarbon feedstock for production of unleaded high-octane gasoline fractions and/or aromatic hydrocarbons WITH6-C10or gasoline and diesel fractions using zeolite catalysts
The invention relates to organic chemistry, in particular to a catalytic process for the production of aromatic hydrocarbons WITH6-C12of hydrocarbons WITH2-C12

The invention relates to methods of producing unleaded high-octane gasoline fractions and/or aromatic hydrocarbons from hydrocarbon and/or oxygen-containing organic compounds
The invention relates to petrochemistry - catalytic process for the production of high-octane gasoline fractions of straight-run petroleum distillates

The invention relates to methods of producing unleaded high-octane gasoline fractions and/or aromatic hydrocarbons from hydrocarbon and/or oxygen-containing organic compounds

The invention relates to the production of motor fuels and can be used in refining and petrochemical industries

The invention relates to the field of oil refining and petrochemistry, namely the composition of the zeolite catalyst conversion on it, aliphatic hydrocarbons2- C12contained in the low-octane straight-run petroleum or gas condensate gasoline fractions, wide fraction of light hydrocarbons, petroleum or waste refinery paraffin and registergui gases, high-octane component of motor gasoline with an octane rating of at least 76 points by the motor method or in a concentrate of aromatic hydrocarbons in stationary or moving layer of granulated or pelletized catalyst

The invention relates to a catalyst and method for the conversion of hydrocarbons of aliphatic C2-C12in high-octane gasoline or concentrate of aromatic hydrocarbons

The invention relates to a hydrodewaxing catalysts straight-run petroleum or gas condensate fractions and how to use it

The invention relates to catalysts for the production of liquid hydrocarbons from dimethyl ether

The invention relates to catalysts and methods for the conversion of aliphatic hydrocarbons to high octane gasoline and aromatic hydrocarbons and can be used in the refining and petrochemical industry

The invention relates to catalysts and methods for their preparation processes for effective removal of nitrogen oxides from waste gases

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons contained in hydrocarbon stock. Catalyst of invention is characterized by that it lowers content of benzene and unsaturated hydrocarbons in gasoline fractions in above isomerization and alkylation process executed in presence of methanol and catalyst based on high-silica ZSM-5-type zeolite containing: 60.0-80.0% of iron-alumino-silicate with ZSM-5-type structure and silica ratio SiO2/Al2O3 = 20-160 and ratio SiO2/Fe2O3 = 30-550; 0.1-10.0% of modifying component selected from at least one of following metal oxides: copper, zinc, nickel, gallium, lanthanum, cerium, and rhenium; 0.5-5.0% of reinforcing additive: boron oxide, phosphorus oxide, or mixture thereof; the rest being alumina. Preparation of catalyst includes following steps: hydrothermal crystallization of reaction mixture at 120-180°C during 1 to 6 days, said reaction mixture being composed of precursors of silica, alumina, iron oxide, alkali metal oxide, hexamethylenediamine, and water; conversion of thus obtained iron-alumino-silicate into H-iron-alumino-silicate; further impregnation of iron-alumino-silicate with modifying metal compound followed by drying operation for 2 to 12 h at 110°C; mixing of dried material with reinforcing additive, with binder; mechanochemical treatment on vibrating mill for 4 to 72 h; molding catalyst paste; drying it for 0.1 to 24 h at 100-110°C; and calcination at 550-600°C for 0.1 to 24 h. Lowering of content of benzene and unsaturated hydrocarbons in gasoline fractions in presence of above catalyst is achieved during isomerization and alkylation of hydrocarbon feedstock carried out at 300-500°C, volumetric feedstock supply rate 2-4 h-1, weight ratio of hydrocarbon feedstock to methanol 1:(0.1-0.3), and pressure 0.1 to 1.5 MPa. In particular, hydrocarbon feedstock utilized is fraction 35-230°C of hydrostabilized liquid products of pyrolysis.

EFFECT: facilitated reduction of benzene and unsaturated hydrocarbons in gasoline fractions and other hydrocarbon fuel mixtures.

3 cl, 1 tbl, 13 ex

Up!