Method of producing high octane gasoline fractions and aromatic hydrocarbons

 

(57) Abstract:

Usage: petrochemistry. The inventive high-octane gasoline fraction and/or aromatic hydrocarbons obtained by refining (possibly in the presence of hydrogen at temperatures calculated 240-480o(Better 320-440oC) and a pressure of 0.1-4.0 MPa (preferably 0.5 to 2 MPa) for the catalyst containing the zeolite pentasil (ZSM-5 or ZSM-11) composition (0,02-0,3) Na2Ol2ABOUT3(0,01-1,13)Fe2O3(27-212)SiO2kH2O modified the elements or compounds of elements I-VIII groups in an amount of 0.01-5.0 wt.%, or zeolite composition (0,02-0,3)Na2Ol2ABOUT3(0,01-0,6)Fe2O3(0,01-1,0)EnABOUTm(28-180)SiO2kH2O,

where enABOUTm- one or two oxide elements II, III, V and VI groups, and k is the corresponding capacity factor, or the zeolite of the composition, the modified elements or compounds of elements I-VIII groups in an amount of 0.01-5.0 wt.%, with further cooling and separation of the products contacting gaseous and liquid fractions by cooling, condensation, separation and rectification. Regeneration of the catalyst (for debinding catalyst coke in order to restore its catalytic properties) Khujand is Sloboda 0.3 to 5 vol.%, and then with oxygen 15-21%. Effect: increase of service life and maintaining a high level of catalyst activity. 5 C.p. f-crystals, 2 tab.

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

Raw material process can be hydrocarbons WITH2-C12and their fractions and/or oxygen-containing organic compounds (alcohols, esters, etc. and mixtures thereof.

High-octane unleaded gasoline at the present time is obtained 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 S.]. 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 structure ZS-5, ZS-11 with specific catalytic properties, the opportunity to develop new processes and the species WITH2to C10and above) and oxygen-containing organic compounds into high-octane gasoline or aromatic hydrocarbons at one stage.

Known methods for processing hydrocarbons WITH2-C10in high-octane gasolines and their components (aromatic hydrocarbons) with the use of catalysts based on zeolites of type ZS-5, ZSM-11 General empirical formula PLR2Ol2O3mSiO2(where n<1 and m>24), including modified elements II, III, IV, V and VIII groups (for example, [U.S. Patent 3953366, CL 01 J 29/06, 1976; 4590323, class C 07 C 2/00, 1986; 4861933, class C 07 C 2/52, 1989; Application CIS countries 0355213, CL 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 200-815oWith pressure of 0.1 to 7 MPa, and the weight rate of feed of 0.05-400 h-1.

To improve properties of zeolite catalysts used zeolites modified with crystal frame, obtained by complete or partial isomorphous substitution of aluminum atoms in alumbramiento the zeolite framework atoms of other elements during their synthesis. So, on the basis of zeolites with isomorphic substitution of atoms of aluminum to chromium atoms, having the General empirical formula AMEn/2CrKinga, dewaxing, reforming, oligomerization, alkylation, isomerization of xylenes [U.S. Pat. France 2463746, CL 01 In 33/20; 01 J 23/86; C 07 C 11/00; With 10 G 11/04, 35/06, 49/04, 1980; U.S. Patent 4299808, CL 01 In 22/20, 1981; 4354924, CL 10 G 11/05, 1982] applied in the environment of the hydrogen-containing gas and hydrogen-free environment.

A method of refining olefins in gasoline and diesel fractions using isomerisation zeolite [U.S. Pat. USA 4861934, class C 07 C 2/02, 1985] . According to this method, the processing of olefins WITH2-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 ZS-5.

A method of obtaining high-octane additives to gasoline, including aromatic hydrocarbons6-C10[Pat. USA 4554396, class 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 bl2ABOUT3Ga2ABOUT3cSiO2, where M is an alkali or alkaline earth metal; is it the cations of various metals.

A method of obtaining gasoline fractions [U.S. Pat. RF 1325892, CL 10 G 11/05, 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 (0,02-0,32)PA2Ol2O3(0,003-2,4)EnABOUTm(28-212)SiO2where enABOUTm- 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 shortcomings of the above described methods are:

- relatively low outputs gasoline fractions;

- relatively low outputs aromatic hydrocarbons;

- relatively low octane number;

- the use of high reaction temperatures;

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

Optimizing the mixing ratio of the zeolite catalysts receive the latest, allowing for processing into high-octane b is oradatabase connection for one phase.

Thus, a method of obtaining aromatic hydrocarbons 6-C10of hydrocarbons and/or alcohols (methanol) using isomerisation zeolites [U.S. Pat. The USSR 936803, class C 07 C 15/02, 1982]. According to this method, the raw material containing hydrocarbon and/or methanol, is subjected to the contacting at a temperature of 350-400oC and a pressure of 0.1-3 MPa catalyst is a crystalline silicate (zeolite). Used zeolite with structure ZS-5 contains in its frame (crystal lattice) isomorphously atoms Fe and/or Fe and Al and has the General empirical formula (0,05-0,30)PA2OF2O3(30-45)SiO2kN2O or (0,11-0,15)PA2Ol2O3(1,22-2,03)Fe2O3(71,1-90,9)SiO2kN2O,

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 gaseous products of the reaction of hydrocarbons WITH1-C4due to high content of iron in the catalyst;

- relatively low-octane gasoline fractions obtained.

The closest in technical essence and the achievable the/SUB>-C10of organic materials on the basis of hydrocarbons and/or oxygen-containing compounds [U.S. Pat. RF 2069227, CL 10 G 35/04, 1996]. According to the selected prototype of the method according to one of its variants is as follows.

Pre-allocated from the gas condensate straight-run gasoline fraction sequentially heated to a temperature close to the temperature of the reaction, the corresponding process equipment (heat exchanger, oven) and served in one of the two shell-and-tube reactors operating alternately in different stages - "reaction" - the contacting of the feedstock with the catalyst and regeneration" - adjustable burning catalyst coke in zakochana catalyst.

At the stage of contacting the feedstock in the reactor serves initially annulus (where it gives up some heat to maintain the process temperature in the tube space of the reactor), and then into the tube space of the reactor loaded with catalyst. In the tube space of the reactor, the raw material is subjected to contact with a fixed bed of the zeolite catalyst at a temperature 320-650oC and a pressure of 0.1-4 MPa. The reaction products are cooled and separated by separation and rectifica columns) on a number of gaseous and liquid fractions, including emitting gasoline fraction containing aromatic hydrocarbons WITH6-C10.

After zakochany mode "reaction" catalyst switches the supply of raw materials spent in the "reaction" of the reactor to the reactor with the reactivated catalyst. In the latter carry out a stage of "reaction", and the reactor zakochany catalyst - step "regeneration". Similar operation switch of the specified flow of raw material from one reactor to another is conducted periodically after zakochany working in the "reaction"of the catalyst.

Regeneration zakoksovanie during the stage of "reaction" of the catalyst is carried out at a temperature of ~550oWith a regenerating gas containing oxygen 10-21%. Stage of catalyst regeneration is carried out by simultaneous supply of pre-heated to 400-450oWith regenerating gas in the tube and in the annulus of the reactor, resulting in the removal of excess heat released during the combustion of catalyst coke in the tube space, and in the coke combustion zone temperature is maintained at regeneration ~550oC.

In the prototype described the application of catalysis is>Al2O3Fe2O352SiO2; with the structure of ZSM-5 General empirical formula of 0.03 PA2Ol2O30,3 Fe2O386SiO2modified with 3 wt.% La or composition of 0.02 PA2Ol2O30,3 GA2O30,1 Fe2O386SiO2modified 0,1% PD.

The main disadvantages of the prototype:

- the use of relatively high temperatures of reaction, which leads to increased energy consumption for production. The necessity of using a relatively high temperature reactions associated with relatively low activity of the catalyst due to not optimal composition of the active centres;

the high oxygen content of the regenerating gas at all stages of catalyst regeneration (10-21 about. %) and high regeneration temperature (550oC). The high oxygen content of the regenerating gas at combustion of catalyst coke leads to increased accordingly stoichiometric, the content of water vapor in the gas, i.e., to increase their partial pressure. It is well known that water vapor at high temperatures lead to dealuminated zeolite framework, resulting in a reduced content of acid centers, leading to the synthesis reaction and the effect of water vapor and increasing regeneration temperature leads to an increase in the degree of dealuminated zeolite framework, therefore, reducing the concentration of acid sites, resulting in reduced level of activity of the catalyst and reduces its service life;

- increased flow of regenerating gas, which is used not only for debinding catalyst coke, but as a refrigerant.

The problem solved by the invention is a method allowing to produce target products at lower temperatures the reaction at the stage interacting with the aim of reducing energy consumption for production, and also allows to reduce the oxygen content at the initial stage of catalyst regeneration with the aim of maintaining the level of catalytic activity of the catalyst and increase its service life.

This object is achieved in that the high-octane gasoline fraction and/or aromatic hydrocarbons WITH6-C10derived from hydrocarbons WITH2-C12and/or oxygen-containing organic compounds (alcohols, esters, and so on ) by pre-heating of raw materials in the respective heat-exchange apparatus to a temperature close to the temperature of the reaction, his contact in the reactor or serial contacting n is the lyst containing zeolite pentasil General empirical formula (0,02-0,3)PA2l2O3(0,01-1,13)Fe2O3(27-212) SiO2kN2O, where k is the appropriate capacity factor, modified by the elements or compounds of elements I-VIII groups in an amount of 0.01-5.0 wt.%, or zeolite General empirical formula (0,02-0,3)PA2Ol2O3(0,01-0,6)Fe2O3(0,01-1,0)EnABOUTm(28-180)SiO2kN2O, where enOm- one or two oxide elements II, III, V and VI groups, and to the corresponding capacity factor, or the zeolite of the composition, the modified elements or compounds of elements I-VIII groups in an amount of 0.01-5.0 wt.%, with further cooling and separation of the products contacting gaseous and liquid fractions in the respective heat exchangers, separators and distillation apparatus, and the regeneration of the catalyst (for debinding catalyst coke in order to restore its catalytic properties) is carried out at a temperature of 450-540oC and a pressure of 0.1-4 MPa initially regenerating gas with an oxygen content of 0.3-5 vol.%, and then with oxygen 15-21% vol.

Depending on the composition of the raw material stage to its contact with catalania feedstock with a catalyst with the rise of reaction temperature with an average rate of 0.2-2 K/h is proportional to the degree of deactivation of the catalyst, thus, in order to maintain the quality and composition of the products at the same level. Possible the implementation stage contacting of the feedstock with the catalyst sequentially in several adiabatic reactors with intermediate supply or removal of heat. Possible the implementation stage contacting of the feedstock with the catalyst in the presence of hydrogen-containing gas. You may receive the regenerating gas by mixing part of the exhaust gas regeneration with air or with air and nitrogen.

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

The main distinctive features of the proposed method are:

the composition of the used catalyst;

- the use of a regenerating gas containing 0.3 to 5% vol. oxygen at the initial stage of regeneration and 15-21% vol. at the final stage catalyst regeneration,

- the possibility of the implementation stage contacting of the feedstock with the catalyst with the rise of reaction temperature with an average rate of 0.2-2 K/h is proportional to the degree of deactivation of the catalyst;

- the possibility of the implementation stage contacting of the feedstock with the catalyst sequentially in several Adia is Tachibana 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;

- implementation stage regeneration of catalyst at low temperatures and with minimal adverse effects on the catalyst water vapor generated at the stage of regeneration by the combustion of catalyst coke.

Achieved results related to the optimization of the composition of the active sites of the zeolite catalyst obtained by a certain ratio of its components and the possibility of reducing the oxygen content in the regeneration gas.

The composition of the crystal lattice of the zeolite and the modification of the catalyst some items I-VIII groups leads to the formation of active sites, leading to the synthesis reaction and conversion of hydrocarbons, such power and concentration, resulting in the implementation of deep transformation of raw materials at lower process temperatures. In addition, the modification of the zeolite and the catalyst for some metals I-VIII groups leads to intensifitsirovany combustion catalyst coke at relatively low temperatures and low oxygen content in d is of burning out the main mass of catalyst coke at the stage of regeneration under reduced oxygen content of the regenerating gas leads to a decrease in the partial pressure of water vapor in the system and, as a consequence, to decrease in extent of dealuminated zeolite framework and the preservation of its level of activity, which generally increases service life of the catalyst. Modification of zeolite and catalyst for some metals I-VIII groups optionally allows you to process raw materials in the presence of hydrogen-containing gas, resulting in a possible increase in yield of the target product and/or increase the duration mezhregionalnogo period of operation of the catalyst and of life.

The implementation of this method is possible using one or more reactors (reactor devices). Their type, the number is largely determined by the processing volume and duration mezhregionalnogo mileage catalyst. For example, when processing 10 tons/year of methanol may use only one shell-and-tube reactor with catalyst loading of 0.8 so When this catalyst has a duration mezhregionalnogo mileage of not less than 600 hours, the duration of stage regeneration is not more than 50 hours, and therefore it is possible to use one reactor in which the initially stage is contacting the feedstock with a catalyst (600 hours), then the stage of regeneration (50 hours), then stage contact and is consistent gasoline type AI-95 at a speed feed 2 h-1the required number of permanent employees catalyst is ~ 6 t, the duration mezhregionalnogo mileage 120-150 hour. For implementing the method requires 2 adiabatic reactors with intermediate heating of the reaction mixture between them (with the total capacity of the catalyst 6 tons). The duration of stage regeneration of catalyst in the adiabatic reactors with consideration of the stages of purging and output temperature of 80-100 hour. Thus, to implement the continuity of the process need 4 adiabatic reactor, 2 of which operate in the production of gasoline, and the other 2 reactor during regeneration of the catalyst.

The essence of the proposed method and its practical applicability is illustrated by the following examples. Examples 1 and 2 illustrate a prototype examples 3-23 - the proposed method.

Example 1. Pre-allocated from the gas condensate straight-run gasoline fraction (FR. 35-140oWith octane PTS= 67 MM) heated to a temperature close to the temperature of the reaction, the corresponding process equipment (heat exchanger, oven) and served in one of the two shell-and-tube reactors operating alternately in different stages of the reactions the coked catalyst.

At the stage of contacting the feedstock in the reactor serves initially annulus (where it gives up some heat to maintain the process temperature in the tube space of the reactor), and then into the tube space of the reactor loaded with catalyst. In the tube space of the reactor at a temperature of 360-370oC, a pressure of 1.0 MPa and the weight of the feed speed 2 h-1the raw material is subjected to contact with a stationary catalyst bed. The catalyst contains 30 wt.% Al2ABOUT3and 70% of the zeolite pentasil structure ZS-11 composition of 0.04 PA2Ol2O3Fe2O352SiO2. The reaction products are cooled and separated into a number of gaseous and liquid fractions by separation and rectification in the corresponding process equipment (heat exchangers, coolers, separators, distillation columns).

In the processing of straight-run gasoline fraction of gas condensate in this way get: high-octane gasoline fraction 81 wt. % residual fraction >160oWith 2% and hydrocarbon gases 17%. High-octane gasoline fraction contains ~25% aromatic hydrocarbons6-C10has an octane number of PTS=76 MM and corresponds never relocat supply of raw materials spent in the "reaction" of the reactor to the reactor with the reactivated catalyst. In the latter carry out a stage of "reaction", and the reactor zakochany catalyst - step "regeneration". Similar operation switch of the specified flow of raw material from one reactor to another is conducted periodically after zakochany working in the "reaction" of the catalyst.

Regeneration zakoksovanie during the stage of "reaction" of the catalyst is carried out at a temperature of ~550oWith a regenerating gas containing oxygen ~ 10 vol.%. Stage regeneration is carried out by feeding the pre-heated up to ~ 400oWith gas simultaneously into the tube and the tube space of the reactor. In the tube space at ~550oWith, is burning the formed coke on the catalyst. Released during the combustion of coke heat partially removed by heating of the regenerating gas passing through the annular space of the reactor.

Example 2. Similar to example 1. As raw materials use methanol-raw (water content of 7%). The contacting of the feedstock with a catalyst containing 70 wt. % modified 3% La3+zeolite pentasil with the structure of ZSM-5 composition of 0.03 PA2Ol2O30,3 Fe2O386SiO2and 30% Al2O3, carried out at tempera 47,7 wt.%; hydrocarbon gases 19,1%, the residual fraction >185oWith 1.7%, gasoline-by 31.5%. The yield of hydrocarbon products: hydrocarbon gases 36,6%, the residual fraction of 3.2%, gasoline fractions of 60.2%. Gasoline fraction contains ~55% of aromatic hydrocarbons WITH6-C10has an octane number of 85 MM and 94 to THEM and meets unleaded gasoline AI-93.

Examples 3-18 illustrate the essence of the proposed method.

Example 3. As a raw material, a mixture of hydrocarbons WITH6-C8containing: n-octane 34 wt.%, the isooctane 33%, cyclohexane 33% and the estimated octane number (OCHp) 52 MM. Raw materials under the pressure of 0.7 MPa pre-heated, evaporated, overheat to a temperature of ~380oWith and put in the volumetric feed rate of the liquid raw material 2.0 hours-1the contacting with the catalyst 1 in shell-and-tube reactor, the heated flue gases. Maintaining the process temperature ~380oWith with an overall endothermic heat effect of the reaction, carried out due to the heat of the flue gases. The composition of the catalyst are given in table. 1.

The reaction products are cooled and share with the allocation of 56 wt.% hydrocarbon gases WITH1-C462% of vysokooktanovye, 51% of isoparaffin, 37% of aromatic hydrocarbons WITH6-C10(including62, C716, P820, WITH9+9), 4% naphthenic, 2% of unsaturated hydrocarbons and has the estimated octane number OCp=96 MM.

Group composition of the products does not change during the 60 hours of overtime, then due process of coke formation is reversible deactivation of the catalyst, leading to a decline in catalyst activity. This results in a reduction of the yield of aromatic hydrocarbons and drop the octane number of the gasoline fraction obtained.

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 vol.% at a pressure of 0.15 MPa heated to a temperature of 370oWith and fed into the reactor with 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% vol. and susestudio contacting the feedstock with the catalyst of example 3 (catalyst 1) is performed with the rise of reaction temperature from ~380oWith up to ~460oWith an average speed of ~0,45 K/h is proportional to the degree of deactivation of the catalyst, maintaining the quality and group composition of the products at the same level. Regeneration of the catalyst is carried out after 180 hours of catalyst. Over 180 hours of catalyst (if the other conditions of example 3) group composition, outputs and quality of the products, similar to example 3, are not changed.

Example 5. As raw materials use of hydrocarbon fraction with PTS= 64 MM, having the following size distribution,oFrom: N. K. 36; about 10.% 65, 50% 107, 90% 152, K. K. 191, and containing hydrocarbons, wt.%: WITH20,1; C30,6; C41,7; C55,5;614,3; C728,7; C828,9; C915,3; C10+4,9. Raw materials under the pressure of 1 MPa is preheated, evaporated, overheat to a temperature of 375oWith and subjected to contacting with the catalyst 2 in the first adiabatic reactor. In the course of a number of chemical reactions, in General, having an endothermic heat effect, the flow of the reaction mixture after the first reactor comes with a temperature of 348oC. the Average reaction temperature in the first reactor is ~360oC. After the first reactor, the reaction mixture is below the practical reactor when the average reaction temperature ~ 360oC. the result of chemical reactions, in General, having an endothermic heat effect, the flow of the reaction mixture after the second reactor comes with a temperature of 346oC. the Volumetric rate of flow of the liquid raw material to the total loading of catalyst in the first and second reactors 1.0 hour-1. The composition of the catalyst 2 are given in table. 1.

The reaction products are cooled and share with the allocation of 30 wt.% hydrocarbon gases WITH1-C4(including liquefied gas WITH3-C418%), 67% of high-octane gasoline fraction and 3% heavy fraction >195oC. high-Octane gasoline fraction contains 8% n-paraffins, 61% of aromatic hydrocarbons WITH6-C10, 30% isoparaffins and naphthenes, 1% of unsaturated hydrocarbons, has an octane number of 86 MM and corresponds to the gasoline AI-95. The yield of aromatic hydrocarbons WITH6-C10of 40.9%.

After a decrease in the activity of the catalyst caused by coke formation processes, resulting in reduced yield of aromatic hydrocarbons and drop the octane number of the gasoline fraction obtained, carry out oxidative regeneration of the catalyst, which consists in burning the formed coke on the catalyst kievit to a temperature of 360oWith and fed into the reactor with 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 propylene. Raw materials under the pressure of 0.5 MPa is heated to a temperature of 260oWith and subjected to contacting with the catalyst 3 in the first adiabatic reactor. In the result of chemical reactions oligomerization and aromatization having an exothermic heat effect, the flow of the reaction mixture after the first reactor comes with a temperature of ~300oC. the Average reaction temperature in the first reactor is ~280oC. After the first reactor, the reaction mixture is cooled to a temperature of 260oWith and subjected to contacting with the same catalyst in the second adiabatic reactor at the average of the temperature of the reaction ~280oC. the result of chemical reactions with an exothermic heat effect, the flow of the reaction mixture after the t to a temperature of 260oWith and subject to the contacts in the third, and after cooling, and in the fourth reactor. Mass feed rate on the total catalyst loading in the first and fourth reactors 2.0 hours-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 35-205oAnd 23% diesel fraction >195oC. Gasoline fraction has a PTSp=76 MM.

Regeneration zakoksovanie catalyst is performed at a pressure of 0.5 MPa initially regenerating gas with oxygen concentration of 1.0 vol.% at a temperature of 450oC, and then 15% vol. at a temperature of 500oC.

Example 7. Similar to example 3. The hydrocarbon fraction WITH6-C8containing, wt.%: n-octane 30, 30 isooctane, cyclohexane 30, toluene 10 and having the estimated octane number (OCHp) 56 MM is subjected to contacting with the catalyst 4 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 at a molar ratio of N2/SN= 6. Products contact share allocation 32% gaseous products, 3% fraction >205oAnd 65% of the gasoline fraction 35-205the ski hydrocarbons WITH6-C1036,4%. The composition of the catalyst are given in table. 1.

Example 8. Similar to example 3 with the difference that stage contacting of the feedstock with catalyst 3 (composition of the catalyst are given in table. 1) is performed with the rise of reaction temperature from ~350oWith up to ~460oWith an average rate of 0.9 K/h is proportional to the degree of deactivation of the catalyst, maintaining the quality and group composition of the products at the same level. In is used as raw material propylene, which is subjected to contacting with the catalyst at a pressure P=0.1 MPa and space velocity of the gaseous raw material v=1050 h-1.

Products contact share with allocation of 31 wt.% hydrocarbon gases, 67% of the gasoline fraction 35-205oWith 2% fraction >205oC. Gasoline fraction containing 4% n-paraffins, 27% isoparaffins and naphthenes, 66% of aromatic and 3% olefinic hydrocarbons and has HDR=88 MM. The yield of aromatic hydrocarbons WITH6-C1044,2%.

Within 120 hours of catalyst group composition, outputs and quality of the products, similar to example 3, are not changed. Regeneration of the catalyst is carried out after 120 hours of operation catalyst. Regeneration zakoksovanie catalyst PR is kind of 5 vol.%, and then about 20%.

Example 9. Similar to example 3. A mixture of 82 wt.% n-hexane and 18% of isopropanol are contacting at T= 360oC, P=1.0 MPa and =2.0 hours-1with catalyst 5 (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 35-205o(Including aromatic hydrocarbons6-C1021,7%) and 1.5% fraction >205oC. the Outputs of the hydrocarbon reaction products in the hydrocarbon part of the amount, wt.%: hydrocarbon gases is 47.5; gasoline fraction 35-205oWith 50,9 (including aromatic hydrocarbons6-C1022,9) and fraction >205oWith 1.6. A gasoline fraction containing 30% of n-paraffins, 22% isoparaffins and naphthenes, 45% of aromatic and 3% of olefinic hydrocarbons.

Example 10. Similar to example 3. The mixture of oxygen-containing compounds containing 70 wt. % methanol and 30% dimethyl ether, subjected to contact at T= 360oWith P=0.5 MPa and =2.0 hours-1with catalyst 5 (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 35-205o(Including aromatic hydrocarbons6 what is wt.%: hydrocarbon gases 33,8; gasoline fraction 35-205oFrom 64.4 (including aromatic hydrocarbons6-C1041,9) and fraction >205oWith 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.

Examples 11-13. Similar to example 3. As a raw material, a mixture of hydrocarbons WITH6-C8containing, by weight. %: n-hexane 30, 30 isooctane, cyclohexane 30, toluene 10 and having the estimated octane number (OCHp) 71 MM. Conditions under contact - reaction temperature (T), pressure (P), the volumetric rate of flow of the liquid raw material (a) used catalyst, the yields of products, the composition of gasoline fractions and their estimated octane number is shown in the table. 2. The compositions of the catalysts are given in table. 1.

Example 14. Similar to example 3. As a raw material, a mixture of hydrocarbons containing 25 wt.% n-pentane and 75% n-hexane and having OCHp=35 MM. The composition of the catalyst 8 are given in table. 1, the process conditions, the yields of products, the composition and OCHpgasoline fractions are given in table. 2.

Examples 15-18. Similar to example 3. As raw materials use a fraction of hydrocarbons WITH6- p
) 56 MM. The compositions of the catalysts ( 9, 10, 11 and 12, respectively) are given in table. 1; the process conditions, the yields of products, the composition and OCHpgasoline fractions are given in table. 2.

Examples 19-23. Similar to example 3. As raw materials use a fraction of hydrocarbons WITH6-C8containing, wt.%: n-hexane 30, cyclohexane 35, toluene, 10, isooctane 25. The compositions of the catalysts ( 13, 14, 15, 16 and 17, respectively) are given in table. 1; the process conditions, the yields of products, the composition of the gasoline fractions are given in table. 2.

1. Method of producing high octane gasoline fractions and/or aromatic hydrocarbons WITH6-C10of hydrocarbons and/or oxygen-containing organic compounds, including pre-heating of raw materials in the respective heat-exchange equipment, it contacts one or more of the reactors at elevated temperatures and pressures of 0.1-4 MPa with a catalyst containing the zeolite pentasil, followed by cooling and separation of the products contacting gaseous and liquid fractions by separation and rectification in the relevant technological devices, including the state of oxidative regeneration of the catalyst oxygen-containing gas at the relevant zeolite General empirical formula (0,02-0,3)Na2Ol2ABOUT3(0,01-1,13)Fe2O3(27-212)SiO2kH2O, where k is the appropriate capacity factor, modified by the elements or compounds of elements I-VIII groups in an amount of 0.01-5.0 wt. % or zeolite General empirical formula (0,02-0,3)Na2Ol2ABOUT3(0,01-0,6)Fe2O3(0,01-1,0)EnABOUTm(28-180)SiO2kH2O, where enABOUTm- one or two oxide elements II, III, V and VI groups, and k is the corresponding capacity factor, or the zeolite of the composition, the modified elements or compounds of elements I-VIII groups in an amount of 0.01-5.0 wt. % and the regeneration of the catalyst is carried out at a temperature of 450-540oC and a pressure of 0.1-4 MPa initially regenerating gas with an oxygen content of 0.3 to about 5. % and then with oxygen 15-21 about. %.

2. The method according to p. 1, characterized in that the contacting of the feedstock with the catalyst is carried out at calculated 240-480oC.

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

4. The method according to PP. 1-3, characterized in that the stage of contacting the feedstock with a catalyst carried out sequentially in several adiabat, what stage of contacting the feedstock with a catalyst is performed with the rise of reaction temperature with an average rate of 0.2-2 K/h is proportional to the degree of deactivation of the catalyst.

6. The method according to p. 1, characterized in that the used regenerating gas obtained by mixing part of the exhaust gas regeneration with air or with air and nitrogen.

 

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The invention relates to petrochemistry - catalytic process for the production of high-octane gasoline fractions of straight-run petroleum distillates

The invention relates to petrochemistry and can be used for processing low-octane gasoline fractions by catalytic reforming unit for producing high-octane gasoline

The invention relates to the isomerization of n-paraffin hydrocarbons and can be used in refining and petrochemical industries

The invention relates to the field of processing hydrocarbon-based aliphatic hydrocarbons, mainly sweet unstabilized gas condensate with a final boiling point 20-190 hail

The invention relates to a method of processing low-octane gasoline fractions by catalytic reforming unit for producing high-octane gasoline

The invention relates to a method of processing low-octane gasoline fractions by catalytic reforming unit for producing high-octane gasoline

The invention relates to the refining and petrochemical industries, in particular to methods of producing high octane gasoline and aromatic hydrocarbons from aliphatic hydrocarbons, C2-C12in the presence of zeolite catalysts

The invention relates to synthetic layered material MCM-56, receiving and use as a sorbent or catalyst component conversion of 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

The invention relates to catalytic chemistry, in particular to the preparation of catalysts based binary oxide systems of the type Me(1)nOmMe(2)p)Ot

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

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