Hydrocarbon feedstock processing method (options)

FIELD: petrochemical processes.

SUBSTANCE: group of inventions relates to processing of hydrocarbon feedstock having dry point from 140 to 400°C and is intended for production of fuel fractions (gasoline, kerosene, and/or diesel) on solid catalysts. In first embodiment of invention, processing involves bringing feedstock into contact with regenerable catalyst at 250-500°C, pressure 0.1-4 MPa, and feedstock weight supply rate up to 10 h-1, said catalyst containing (i) crystalline silicate or ZSM-5 or ZSM-14-type zeolite having general empiric formula: (0.02-0.35)Na2O-E2O3-(27-300)SiO2-kH2O), where E represents at least one element from the series: Al, Ga, B, and Fe and k is coefficient corresponding to water capacity; or (ii) silicate or identically composed zeolite and at least one group I-VIII element and/or compound thereof in amount 0.001 to 10.0 % by weight. Reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-4 MPa. Hydrocarbon feedstock utilized comprises (i) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of isoparaffins and naphtenes in summary amount 54-58.1%, aromatic hydrocarbons in amount 8.4-12.7%, and n-paraffins in balancing amount; or (ii) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of following fractions, °C: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272. In second embodiment, feedstock boiling away up to 400°C is processed in presence of hydrogen at H2/hydrocarbons molar ratio between 0.1 and 10 by bringing feedstock into contact with regenerable catalyst at 250-500°C, elevated pressure, and feedstock weight supply rate up to 10 h-1, said catalyst containing zeolite having structure ZSM-12, and/or beta, and/or omega, and/or zeolite L. and/or mordenite, and/or crystalline elemento-aluminophosphate and at least one group I-VIII element and/or compound thereof in amount 0.05 to 20.0 % by weight. Again, reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-6 MPa.

EFFECT: improved flexibility of process and enlarged assortment of raw materials and target products.

12 cl, 3 tbl, 22 ex

 

The present invention relates to a method of processing hydrocarbon material having a temperature of end boiling point of 140 to 400°C, to obtain the fuel fractions of gasoline, kerosene and/or diesel fractions, using solid catalysts.

The traditional raw material for producing high-octane gasoline, jet fuel and diesel fuels are the different fractions of crude oils and gas condensates. High-octane gasolines normally receive or process of cracking hydrocarbon fractions, wikipaedia above 300°or processes of reforming, isomerization [Gureev A.A., Zhorov, Y.M., Smidovich EV Production of high-octane gasoline. - M, - Chemistry, 1981, - 224 C.] and reforming [Stepanov V.G., Jonah KG - Chemistry and technology of fuels and oils, 2000, No. 1, pp.8-12] gasoline or naphtha fractions, wikipaedia to 150-250°C.

Kerosene and diesel fractions are often obtained by distillation of crude oil or gas condensate with the allocation of appropriate straight-run fractions. Under certain of their properties, they can be directly used respectively as jet fuel and diesel fuel. With the increased content of total sulphur straight-run fractions subjected to gray - or Hydrotreating to reduce the total sulfur content and a product of the required quality [Manovan A.K. Technology the Oia primary processing of oil and natural gas. - M, Chemistry, 2001, - 568 S.].

Known methods of processing hydrocarbon wide fractional composition comprising gasoline and diesel fractions. Thus, according to [U.S. Pat. Of the Russian Federation No. 2059688, CL 10G 69/02, 10G 45/02, 1996], hydrocarbons - diesel fraction together with a mixture of gasoline and light gas oil coking is subjected to Hydrotreating followed by separation of the reaction products from the gaseous products, gasoline and diesel fuel. The main disadvantage of this method is that the resulting gasoline fraction has a low octane number and cannot be used as gasoline.

The closest in technical essence and the achieved effect is a method of processing petroleum distillates [U.S. Pat. Of the Russian Federation No. 2181750, CL 10G 35/095, 2002]. In accordance with the selected prototype gasoline with an octane rating no lower than 80 MM are obtained by conversion of petroleum distillate fractions with temperature end of the boil to 200-400°on the porous catalyst at a temperature of 250-500°C, pressure of not more than 2 MPa and mass feed rate of the substrate is not more than 10 h-1. As the catalyst used zeolites with structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, beta with a molar ratio of SiO2/Al2O3not exceeding 450 or gallosilikata, haloaluminate, gelatoria, prosilica, chrome is alumosilicate with the above structures, or alumophosphate structure AIPO-5, AIPO-11, AIPO-31, AIPO-36, AIPO-37, AIPO-40, AIPO-41 with the entered items selected from a number of: Mg, Zn, Ga, Mn, Fe, Si, Co, Cd. It is possible to use catalysts containing the above system and up to 10% wt. compounds of at least one of the following metals: Zn, Ga, Ni, Co, Mo, W, Re, rare earth elements, platinum group metals.

The main disadvantage of the prototype is the low range of products - production of high-octane gasoline fractions with temperature end boiling point not higher than 195°With, while modern domestic standards limit the temperature of the end of the gasoline boiling 215° [GOST R 51105-97, GOST R 51313-99].

The problem solved by the present invention is to provide a method of processing hydrocarbon material, which can increase the flexibility of the process with the aim of expanding the range of the obtained target products: high-octane gasoline (including gasoline) and heavy distillate fractions, including kerosene or diesel fraction, and to increase the operating time of the catalyst.

The task can be achieved by either of the two following main options.

On the first one, this object is achieved in that the hydrocarbon processing, wikipaedia to 400°, carried out by E. what about the contact at pressures of 0.1-4.0 MPa, the temperature of 250-500°and mass feed rate of the raw material up to 10 h-1regenerated catalyst products contact after cooling divided by separation and/or distillation of the fraction(s) of hydrocarbon gases, gasoline and kerosene and/or diesel fraction, the regeneration of the catalyst to carry out oxygen-containing gas at a temperature of 350-600°and a pressure of 0.1-4 MPa, and the catalyst contains crystalline silicate or zeolite with structure of ZSM-5 or ZSM-11 General empirical formula (0,02-0,35)Na2O·e2O3·(27-300)SiO2·kH2O, where e is at least one element of a number of Al, Ga, In, Fe, a k - appropriate capacity factor, or contains the specified composition of the silicate or zeolite and at least one element and/or the connection element I-VIII groups in an amount of 0.01 to 10.0 wt.%.

On the second version this object is achieved in that the hydrocarbon processing, wikipaedia to 400°, carried by the probe at a pressure of 0.1 to 6.0 MPa, a temperature of 250-500°and mass feed rate of the raw material up to 10 h-1regenerated catalyst in the presence of hydrogen at a molar ratio of N2/hydrocarbons - 0,1-10 products contact after cooling divided by separation and/or distillation of the fraction(s) of the hydrocarbon gas is in, gasoline and kerosene and/or diesel fraction, the regeneration of the catalyst to carry out oxygen-containing gas at a temperature of 350-600°and a pressure of 0.1 to 6.0 MPa.

For any of the two embodiments of this method further and perhaps the following in any combination:

- implementation stage contacting of the feedstock with the catalyst with the rise of reaction temperature with an average speed of 0.01-2 °C/h;

- implementation of the regeneration of the catalyst initially regenerating gas with an oxygen content of 0.1-5% vol., and then with oxygen 7-21% vol.;

- getting regenerating gas by mixing part of the exhaust gas regeneration with air or with air and nitrogen;

- use as raw material fractions of crude oil or gas condensate or fractions of gas condensate, or products of processing of oil or gas condensate fractions, or other hydrocarbon fractions containing paraffinic and/or naphthenic and/or aromatic hydrocarbons;

- implementation stage contacting of the feedstock with the catalyst together with additionally supplied registertask factions and/or oxygen-containing organic compounds.

According to the second variant of the method (using the hydrogen-containing gas) it is possible to use a catalyst containing cristalli the definition silicate or zeolite with structure of ZSM-5 or ZSM-11 and/or ZSM-12, and/or β (β), and/or Ω (omega), and/or zeolite L (El), and/or mordenite and/or crystalline elementalist and containing at least one element and/or the connection element I-VIII groups in the amount of 0.05 to 20.0% by wt.

The main distinctive features of the proposed method are:

- in the first embodiment (in the case of hydrogen-free processing):

- separation of the reaction products by separation and/or rectification;

- the use of the regenerated catalyst particular composition and implementation stage of catalyst regeneration;

- second option:

- implementation stage of contacting the raw material with regenerated catalyst in the presence of hydrogen;

- separation of the reaction products by separation and/or rectification;

- the use of the regenerated catalyst and the implementation stage of its regeneration;

- the possibility of using a catalyst containing a zeolite with structure type zeolites ZSM-12, and/or beta and/or omega, and/or zeolite L, and/or mordenite and at least one element and/or the connection element I-VIII groups in the amount of 0.05 to 20.0% by wt.

for both options:

- ability to carry out the stage of contacting the feedstock with a catalyst with the rise of reaction temperature with an average speed of 0.01-2 °C/h;

- ability to carry out the stage of contacting Ira with catalyst together with additionally supplied registertask factions and/or oxygen-containing organic compounds.

The main advantages of the proposed method are:

- expanding the range of products - it is possible to produce high-octane gasoline fractions, kerosene and diesel fractions with low temperature pour point and low content of total sulfur;

- expansion of the range of processed raw materials;

- increase the duration mezhregionalnogo period of operation of the catalyst.

Achieved results related to the optimization of composition involved in the reactions of breaking of C-C and C-S links active centers of the catalyst, forming a component part. Variation of the catalyst composition, and the composition of zeolites allows you to ensure the presence of active centers involved in the reactions of conversion of higher hydrocarbons, C5+and thus change the composition and quality of the distillate fractions and to make high-octane gasoline fraction and a kerosene or diesel fraction with low temperatures of cloud and pour point (i.e. to expand the range of manufactured products) and low total sulfur content.

The use of hydrogen allows to process hydrocarbon fraction having a temperature of an end boiling point of 140 to 400°With higher duration mezhregionalnogo period of operation of the catalyst, which increases its service life and improve, processing of sulfur-containing raw material, the degree of desulfurization of the target product. Modification of the catalyst for some items and/or their compounds additionally enables to achieve greater depth cleaning of sulfur-containing hydrocarbon fractions of the total sulfur.

The method is as follows. Raw materials or raw material in a mixture with hydrogen-rich recycle gas, possibly mixed with registertask factions and/or oxygen-containing compounds is heated to a temperature of the processing in the respective processing units (heat exchangers, furnaces and the like) and in the reactor(s) at a temperature of 250-500°C, a pressure of 0.1 to 6.0 MPa and mass feed rate of the raw material up to 10 h-1subjected to contact with periodically regenerated catalyst. Can be used in different types of reactor systems with stationary or moving, or fluidized bed of catalyst.

The optimal process parameters (temperature, pressure, feed rate) are determined depending on the type of catalyst, composition of the feedstock and the type of produce target products. The average reaction temperature may be approximately the same in all operating reactors or different. To increase the duration mezhregionalnogo mileage catalyst, which depends on the type of raw materials and usloviiakh, it is possible to increase the reaction temperature to maintain the quality and group composition of the products at the same level.

The reaction products are cooled in the corresponding process equipment (heat exchangers, refrigerators, etc. and divide by separation and/or distillation with gaseous fractions, including liquefied natural gas, and depending on the range of products, various liquid fractions, for example:

- gasoline fraction <215°With (or gasoline) and fraction >215°C;

- gasoline fraction NK - 150°With, a kerosene fraction 150-250°With (or jet fuel) and fraction >250°With (if the latter is available);

- gasoline fraction NK - 150°C, diesel fraction 150-350°With (or diesel fuel) and fraction >350°With (if the latter exists).

In General, the range of possible products (high-octane gasoline fraction and a kerosene or diesel fraction) depends on the content in the raw material corresponding fractions and the process conditions.

During the processing of hydrocarbons on the catalyst processes coke formation, leading to reversible deactivation of the catalyst, resulting in a lower level of activity. To restore the activity level of the catalyst periodically carry out its oxidative regeneration, in which survival is assured formed on the catalyst coke oxygen-containing gas.

Stage of catalyst regeneration is carried out at a temperature of 350-600°and a pressure of 0.1 to 6.0 MPa initially regenerating gas with an oxygen content of 0.1-5% vol., and then, as the combustion of the main part of coke with oxygen 7-21% about. 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 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. Used crystal elementalist have the structure of SAPO-5, SAPO-11, SAPO-31, etc.

As the process feedstock use any hydrocarbon fraction having a temperature of end boiling between 140°With up to 400° - fractions of oil, gas condensate and its fractions, refined products of petroleum or gas condensate fractions and other hydrocarbon fractions (e.g., products of the Fischer-Tropsch process and the like).

The essence of the proposed method and its practical applicability is confirmed by the following example is mi. Examples 1-13 illustrate the possibility of hydrocarbon processing without the use of hydrogen, examples 14-22 - in the presence of hydrogen-containing gas.

Example 1. In is used as raw material gas condensate having the following size distribution, °S: NK - 27; 10% about. - 59, 50% - 114, 90% - 234, KK - 252 and containing hydrocarbons, wt.%: paraffins3-C4- 7,8; n-paraffins C5+- 26,5; ISO and naphthenes With5+- 54,1; aromatic With6+and 11.6. The raw material is preheated to a temperature of the processing and at a temperature of 360°C, pressure of 1.0 MPa and a mass flow rate of feed of 1.0 h-1subjected to contacting with the catalyst No. 1. The composition of the catalyst is summarized in table 1.

The reaction products are cooled and separated by separation and rectification emitting 28,3% wt. hydrocarbon gases C1-C4(including liquefied gas With3-C4is 21.8%), 67.6% of high-octane gasoline fraction NC-215°and 4.1% fraction >215°C. high-Octane gasoline fraction contains a 10.2% n-paraffins, 45.5% of aromatic hydrocarbons, 42,5% isoparaffins and naphthenes, 1.8% of unsaturated hydrocarbons has an octane rating of 82 MM and 91 to THEM and meets the gasoline AI-91.

After a decrease in the activity of the catalyst caused by coke formation processes, resulting in reduced yield of aromatic using hydrocarbon and drop the octane number of the gasoline fraction obtained, spend oxidative regeneration of the catalyst, which consists in burning the formed coke on the catalyst oxygen-containing gas. Regeneration zakoksovanie catalyst is carried out at a pressure of 1.0 MPa initially at a temperature of 450°by submitting a regeneration gas oxygen content of 0.5% vol., and after burnout of the main part of catalyst coke at a temperature of 520°and the oxygen content of 15% vol.

Examples 2-4. Similar to example 1. The compositions of the used catalysts are shown in table 1, the contact conditions, the yields and characteristics of the resulting gasoline in table 2.

Example 5. As raw materials use of straight-run gasoline fraction oil, having the following size distribution, °S: NK - 32; 10% about. - 53, 50% - 101, 90% - 132, KK - 154 and containing hydrocarbons, wt.%: paraffins3-C4- 1,1; n-paraffins With5+- 32,1; ISO and naphthenes, C5+at 58.1; aromatic With6+an 8.4. The raw material is preheated and at a temperature of 360°C, pressure of 1.0 MPa and a mass flow rate of feed of 2.0 h-1subjected to contacting with the catalyst No. 5. The composition of the catalyst is summarized in table 1.

The reaction products are cooled and separated by separation and rectification emitting 31,7% wt. hydrocarbon gases C1-C4(including liquefied gas With3-C brand LPG - 23,8%), with 66.5% of high-octane gasoline fraction NC-215°and 1.8% fraction >215°C. high-Octane gasoline fraction contains ˜8% n-paraffins, ˜46% of aromatic hydrocarbons, ˜45% isoparaffins and naphthenes, ˜1% of unsaturated hydrocarbons has an octane rating of 83 MM and 92 to THEM and meets the gasoline AI-92.

Group composition of the products does not change during the 45 hours of processing, after which, due to the process of coke formation is reversible deactivation of the catalyst, leading to a decline in catalyst activity. After a decrease in the activity of the catalyst, 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 oxygen-containing gas.

Regeneration zakoksovanie catalyst is carried out at a pressure of 0.2 MPa initially at a temperature 480°by submitting a regeneration gas oxygen content of 5.0% vol., and after burnout of the main part of catalyst coke at a temperature of 550°and the oxygen content of 21% vol.

Example 6. Similar to example 5 with the difference that stage contacting of the feedstock with catalyst No. 5 is carried out with the rise of temperature reacts and from 360° With up to 450°With an average speed of 2 °C/hour in proportion 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 5) group composition, outputs and quality of the products, similar to example 5, are not changed.

Example 7. Similar to example 5. Catalyst No. 5 and under the conditions of example 5 is carried out the transformation of raw materials, consisting of 88% by weight. straight-run gasoline fractions shown in example 5 composition and 12% olefins. After separation of the reaction products get to 24.6% wt. hydrocarbon gases C1-C4(including liquefied gas With3-C4brand LPG - 18,5%), 73.2 per cent of high-octane gasoline fraction NC-215°and 2.2% fraction >215°C. high-Octane gasoline fraction contains ˜8% n-paraffins, ˜46% of aromatic hydrocarbons, ˜44% isoparaffins and naphthenes, ˜1% of unsaturated hydrocarbons has an octane rating of 82 MM and 92 to THEM and meets the gasoline AI-92.

Example 8. Similar to example 5. The transformation of raw materials shown in example 5 composition carried out on the catalyst No. 6 in the presence of added to the raw material methanol and n-propanol at a ratio of 8:1:1 mass. respectively. After cooling and razdelnopolye reactions get 8,6% wt. water 13,0% hydrocarbon gases C1-C4(including liquefied gas With3-C4brand LPG - 9,8%), 77.1 percent of high-octane gasoline fraction NC-215°and 1.3% fraction >215°C. the Composition of the catalyst is summarized in table 1, the contact conditions, the yields of products in the hydrocarbon portion and characteristics of the resulting gasoline - 2.

Example 9. As raw materials use of straight-run gasoline fraction of gas condensate with a total sulfur content of 0.29 wt.%, with the following fractional composition, °S: NK - 43; 10% about. - 92, 50% - 124, 90% - 165, KK - 195 and containing hydrocarbons, wt.%: paraffins3-C4- 0,7; n-paraffins C5+- 30,8; ISO and naphthenes, C5+- 55,8; aromatic With6+- 12.7mm. The raw material is preheated and at a temperature of 400°C, a pressure of 1.5 MPa and a mass flow rate of feed of 4.2 h-1subjected to contacting with the catalyst No. 7. The composition of the catalyst is summarized in table 1.

The reaction products are cooled and separated by separation and rectification emitting 26,3% wt. hydrocarbon gases C1-C4(including liquefied gas With3-C4- 21,6%), and 71.4% for high-octane gasoline fraction NC-215°and 2.3% fraction >215°C. high-Octane gasoline fraction has a content of total sulfur 0,008%, contains 6.4% of n-paraffins, 45.2% of aromatic hydrocarbons, 48,4% isoparaffins and naphthene is in, has an octane rating of 84 MM and 92 to THEM and meets the gasoline AI-92.

Regeneration of the catalyst is carried out at a pressure of 1.0 MPa initially at a temperature of 500°by submitting a regeneration gas oxygen content of 1.5% vol., and after burnout of the main part of catalyst coke at a temperature of 520°and the oxygen content of 10%. Regenerating gas is produced by mixing part of the exhaust gas regeneration supplied to the recirculation, air and nitrogen.

Examples 10-11. Similar to example 9. The compositions of the used catalysts are shown in table 1, the contact conditions, the yields and characteristics of the resulting gasoline in table 2. The total sulfur content in the resulting gasoline is: 0.035% of wt. for example 10 and 0,016% wt. in example 11.

Example 12. As raw materials use of straight-run fraction of gas condensate with a total sulfur content of 0.04 wt.%, having a density of 791 kg/m3the pour point -42°and the following fractional composition, °S: NK - 151; 10% about. - 162, 50% - 189, 90% - 241, KK - 267. The raw material is heated to a temperature of processing and at a temperature of 320°C, pressure of 1.0 MPa and a mass flow rate of feed 2.5 h-1subjected to contacting with the catalyst No. 10. The composition of the catalyst is summarized in table 1.

The reaction products are cooled and separated by rectification highlighted the eat to 12.0 wt.%. hydrocarbon gases With1-C4(including liquefied gas With3-C4- 9,6%), 52.4% of high-octane gasoline fraction of NC-150°and 35.6% for kerosene fraction 150-270°C. Kerosene fraction contains 0.01% of the total sulfur, has a pour point below - 60°and corresponds to the jet fuel T-1. High-octane gasoline fraction contains 17.5% of n-paraffins, 27.8 percent aromatic hydrocarbons, 53,1% isoparaffins and naphthenes, has an octane number 84 to THEM, the content of total sulfur less than 0.01%.

Regeneration of the catalyst is carried out at a pressure of 1.0 MPa initially at a temperature of 520°by submitting a regeneration gas oxygen content of 1.5% vol., and after burnout of the main part of catalyst coke at a temperature of 550°and the oxygen content of 7% vol.

Example 13. As raw materials use distillate fraction of crude oil with a total sulfur content of 0.1 wt.%, having a density of 809 kg/m3the pour point of - 28°and the following fractional composition, °S: NK - 130; 10% about. - 161, 50% - 239, 90% - 339, KK - 364. The raw material is preheated and at a temperature of 360°C, pressure of 1.0 MPa and a mass flow rate of feed of 2.6 h-1subjected to contacting with the catalyst No. 11. The composition of the catalyst is summarized in table 1.

The reaction products are cooled and separated by rectification emitting 17,6% wt. the hydrocarbon is s gas C 1-C4(including liquefied gas With3-C4- 14,1%), 45.8% of the gasoline fraction of NC-150°and 36,4% diesel fraction 150-365°or 20.4% kerosene fraction 150-250°and 16.2% of the heavy diesel fraction >250°C.

Derived kerosene fraction contains 0,006% total sulfur, has a pour point below -60°and corresponds to the jet fuel T-1. Gasoline fraction contains 16.7% of n-paraffins, 29.3% of aromatic hydrocarbons, 54,0% isoparaffins and naphthenes, has an octane number 84 to THEM, the content of total sulfur less than 0,004%. Diesel fraction >250°corresponds With diesel fuel diesel fuel.

Regeneration of the catalyst is carried out at a pressure of 1.0 MPa initially at a temperature of 500°by submitting a regeneration gas oxygen content of 1.5% vol., and after burnout of the main part of catalyst coke at a temperature of 540°and the oxygen content of 20% vol.

Example 14. As raw materials use of straight-run diesel fraction, gas condensate with a total sulfur content of 0.34 wt.%, having a congealing point of -32°and the following fractional composition, °S: NK - 168; 10% about. - 189, 50% - 236, 90% - 314, KK - 345. The raw material is preheated and at a temperature of 360°C, pressure of 1.0 MPa and a mass flow rate of feed of 2.4 h-1subjected to contacting with the catalyst No. 12 in the presence of wodorosoda the future of gas at a molar ratio of H 2/hydrocarbons to 3.8. The composition of the catalyst is summarized in table 1.

The reaction products are cooled and separated by separation and rectification emitting hydrogen-containing gas and 25.9% wt. hydrocarbon gases C1-C4, 39.2% of gasoline fraction of NC-150°and 34.9% of diesel fraction 150-345°or 25.8% of the kerosene fraction 150-250°and 9.1% heavy diesel fraction 250-345°C. Gasoline fraction contains 12.5% of n-paraffins, 28.8% of aromatic hydrocarbons, 58,7% isoparaffins and naphthenes, has an octane number of 85 THEM, and the content of total sulfur in it is 0,006% wt. Diesel fraction 150-345°has a pour point of -48°With, a kerosene fraction is below -60°C.

Regeneration of the catalyst is carried out at a pressure of 1.0 MPa initially at a temperature of 500°by submitting a regeneration gas oxygen content of 5% by vol., and after burnout of the main part of catalyst coke at a temperature of 520°and the oxygen content of 15% vol.

Example 15. As raw materials use of hydrocarbon fraction is a liquid product of the Fischer-Tropsch process having the following size distribution, °S: NK - 26, 10% about. - 36, 50% - 75, 90% - 216, KK - 264. The raw material is preheated and at a temperature of 250°C, a pressure of 3.0 MPa and a mass flow rate of feed of 5.0 h-1subjected to contacting with the catalyst No. 13 in the presence of water the ode at a molar ratio of H 2/hydrocarbons is 0.1. The composition of the catalyst is summarized in table 1.

The reaction products are cooled and separated by separation and rectification emitting hydrogen gas, hydrocarbon gas C1-C4gasoline fraction C5-150°C, a kerosene fraction 150-260°and fraction >260°C. the yields of products are, % wt.: hydrocarbon gases C1-C4- 8,4; gasoline fraction C5-150° - 44,8; kerosene fraction of 41.6; fraction >260° - 5,2.

Regeneration of the catalyst is carried out at a pressure of 0.2 MPa and a temperature of 450°originally regenerating gas with an oxygen content of 5% by vol. After burnout of the main part of the catalyst coke content of oxygen in the regenerating gas is increased up to 20-21%. and carry out the regeneration of the catalyst at a temperature of 480-520°C.

Example 16. Similar to example 15. Raw material of example 15 is subjected to contacting with the catalyst No. 14 at a temperature of 280°C, a pressure of 3.0 MPa, mass flow rate of feed of 2.0 h-1and a molar ratio of H2/hydrocarbons is 0.1. The composition of the catalyst is summarized in table 1. The yields of products are, % wt.: hydrocarbon gases C1-C4- 9,8; gasoline fraction C5-150°C - 35,3; kerosene fraction - 44,4; fraction >260°to 10.5.

Examples 17-22. As raw materials use of model mixture ug is evagorou, containing 75 wt.%. n-hexadecane and 25% o-xylene, wikipaedia in the interval 144-272°C. the Raw material is heated to a temperature of processing and subjected to contact with a catalyst at elevated temperature and pressure in the environment of hydrogen. The reaction products are cooled and separated by separation and rectification emitting hydrogen gas, hydrocarbon gas and, depending on necessity, a gasoline fraction With5-C9or C5-C12, kerosene or diesel fraction. The compositions of the used catalysts are shown in table 1, the contact conditions and the possible outputs of the products in table 3.

Regeneration of the catalyst is carried out analogously to example 15.

Table 1.

The compositions of catalysts for conversion of hydrocarbons to examples No. 1-22.
No. catalystThe composition of the catalyst (zeolite, its composition, the amount of binder and modifier element)Structure type zeolite
165%(0,32Na2O·Al2O3·O 46Fe2O3·0,3Ga2O3·108SiO2)+35%Al2O3ZSM-5
2[70%(0,03Na2O·Al2O3·0,3Fe2O3·88SiO2 )+30%Al2O3]+0.3%of Mn+0.05%of LaZSM-5
30,07Na2O·Ga2O3·0,01F2O3·73SiO2ZSM-5
4(0,04Na2O·Al2O3·0,04Fe2O3·82SiO2)+1,0%ZrZSM-11
5[70%(0,03Na2O·Al2O3·0,3Fe2O3·88SiO2)+30%Al2About3]+0.05%of LaZSM-5
6[70%(0,09Na2O·Al2O3·0,3Fe2O3·96SiO2)+30%Al2O3]+0,5%Zn and 0.5%CrZSM-5
7[70%(0,04Na2O·Al2O3·1,13Fe2O3·212Si)+30% Al2O3]+3,0%PZSM-5
870%(0,04Na2O·Al2O3·0,45Fe2O3·0,05B2O3·92SiO2)+30%Al2O3ZSM-11
9[70%(0,04Na2O·Al2O3·0,15Fe2O3·94SiO2)+30%Al2O3]+0,5%CoS+1,5%MoS3ZSM-5
1070%(0,02Na2O·Fe2O3·144SiO2)+30%Al2O3ZSM-5
1160%(0,02Na2O·Al2O3·0,01Fe2O3·24SiOsub> 2)+40%SiO2ZSM-5
1250%[(0,04Na2O·Al2O3·46SiO2)+0,3%La]+10%MoO3+5%NiO+2%2O3+33%Al2O3ZSM-5
13(0,19Na2O·Al2O3·9,05SiO2)+0,05%PtQ
14(0,12Na2O·Al2O3·0,01Fe2O3·16,1SiO2)+0,1%Pdthe mordenite
15(0,03Na2O·Al2O3·0,1Fe2O3·84SiO2)+0.5%of Pd+0,18%Cr+0,23%Caβ
16(0,03Na2O·Al2O3·0,1Fe2O3·84SiO2)+0.5%of Pd+0,18%Crβ
17(0,03Na2O·0,03K2O·Al2O3·8,3SiO2)+0.5%of Pd+0.2%Of CrL
18(Al2O3·P2O3·0,2SiO2)+0,4%Pd+0,1%CrSAPO-11
19(0,05Na2O·Al2O3·132SiO2)+0.5%of Pd+0.2%Of CrZSM-12
20(Al2O3·1,1R2O3·0,2SiO2)+0,4% Pd+0,1%Cr+0,11%CaSAPO-31

Table 2.

Reaction conditions and o the dy products according to examples 1-11.
no examplesCatalyst No. 1The reaction temperature, °Pressure, MPaFeed rate, h-1Yield, % wt.The composition of gasoline, wt.%The octane number of gasoline, MI
gas C1-C4gasoline, FR. NC-215°fraction >215°n-paraffinsaromaticISO + naphthenes*
113801,53,028,367,64,110,245,544,391
223601,01,132,663,6the 3.86,955,2of 37.996
333201,02,2the 10.186,43,5of 17.524,4to 58.181
443401,02,29,8of 87.03,215,928,0 56,184
553601,02,031,766,51,87,946,345,892
753601,02,024,673,22,28,245,645,292
864200,58,014,284,31,511,134,054,986
974001,54,226,371,42,36,445,248,692
1083601,02,114,784,01,310,033,356,785
1193802,02,220,1to 78.31,68,339,652,188
*Olefin content less than 2% wt. and is included in a faction ISO and nafta the s".

9,8
Table 3.

Reaction conditions and the yields of products in examples 17-22
no examples171819202122
Catalyst No. 1151617181922
The reaction temperature, °300260380340340380
Pressure, MPa3,05,03,03,03,03,0
Mass feed rate, h-12,01,52,53,03,02,0
A molar ratio of N2/SN579995
The degree of conversion n-C16, %97,669,293,785,986,482,3
Output fractions, % wt.:
- C1-C46,211,8the 13.42,32,9
- C5+90,293,888,286,697,7to 97.1
- C5-C1288,267,581,171,640,734,4
- C10+2,629,19,017,168,270,7
- ISO C5-C9of 57.5to 43.144,245,810,47,4
'n-paraffins C5-C916,910,2of 17.513,63,73,5
- ISO C5-C1257,744,644,846,919,012,6
'n-paraffins C5-C12of 17.010,617,714,05,55,3
- ISO10+0,44,32,65,253,552,8
'n-paraffins With10+1,923,95,311,3 13,916,9
- ISO C13+0,22,82,04,144,947,6
'n-paraffins C13+1,823,55,110,912,115,1
aromatic With6-C104,68,811,3the 5.78,59,5
- naphthenic6-C108,93,57,35,07,77,0

1. A method of processing hydrocarbon feedstock by contacting at a pressure of 0.1 to 4 MPa, a temperature of 250-500°and mass feed rate of the raw material up to 10 h-1regenerated catalyst containing a crystalline silicate or zeolite with structure of ZSM-5 or ZSM-11, General empirical formula (0,02-0,35)Na2O·e2O3·(27-300)SiO2·kH2O, where e is at least one element of a number of Al, Ga, In, Fe, a k - appropriate capacity factor, or with the catalyst containing the silicate or zeolite of the composition, and at least one element and/or the connection element I-VIII groups in an amount of 0.01-10.0 wt.%, separation of the products contact after cooling p is the separation and/or distillation of the fraction(s) of hydrocarbon gases, gasoline, kerosene and/or diesel fraction, the regeneration of the catalyst to carry out oxygen-containing gas at a temperature of 350-600°and a pressure of 0.1-4 MPa, characterized in that is used as raw material hydrocarbon fraction, wikipaedia to 400°and containing ISO and naphthenes in the total number 54-58,1 wt.%, aromatic hydrocarbons - 8.4 to 12.7 wt.%, paraffins and n-paraffins - the rest up to 100 wt.% or used as raw material hydrocarbon fraction, wikipaedia to 400°and selected from groups having the following intervals boiling fractions, °S: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272.

2. The method according to claim 1, characterized in that the stage of contacting the feedstock with the catalyst is carried out in the presence of hydrogen at a molar ratio of H2/hydrocarbons - 0,1-10.

3. The method according to claim 1, characterized in that the stage of contacting the feedstock with a catalyst is performed with the rise of reaction temperature with an average speed of 0.01 to 2 deg./PM

4. The method according to claim 1, characterized in that the regeneration of the catalyst is carried out initially regenerating gas with an oxygen content of 0.1-5 vol.%, and then with oxygen 7-21%vol.

5. The method according to claim 1, characterized in that the regenerating gas is produced by mixing part of the exhaust gas regeneration with air or with air and nitrogen.

6. The method according to claim 1, great for the present, however, what stage contacting of the feedstock with the catalyst to carry out together with additionally supplied olefin-containing fractions and/or oxygen-containing organic compounds.

7. A method of processing hydrocarbon material in the presence of hydrogen at a molar ratio of H2/hydrocarbons - 0,1-10 by contact with excessive pressure, a temperature of 250-500°and mass feed rate of the raw material up to 10 h-1regenerated catalyst containing zeolite and possibly containing metals or their compounds, separation produktov contact after cooling by separation and/or distillation of the fraction(s) of hydrocarbon gases, gasoline, kerosene and/or diesel fraction, the regeneration of the catalyst to carry out oxygen-containing gas at a temperature of 350-600°and a pressure of 0.1 to 6 MPa, characterized in that the catalyst contains a zeolite with structure of ZSM-12, and/or β (β), and/or Ω (omega), and/or zeolite L (El), and/or mordenite and/or crystalline elementalist, and it contains at least one element and/or the connection element I-VIII groups in the amount of 0.05 to 20.0 wt.%, and is used as raw material hydrocarbon fraction, wikipaedia to 400°C.

8. The method according to claim 7, characterized in that the stage of contacting the feedstock with the catalyst is carried out at davlenie,1-6 MPa.

9. The method according to claim 8, characterized in that the stage of contacting the feedstock with a catalyst is performed with the rise of reaction temperature with an average speed of 0.01 to 2 deg./PM

10. The method according to claim 8, characterized in that the regeneration of the catalyst is carried out initially regenerating gas with an oxygen content of 0.1-5 vol.%, and then with oxygen 7-21%vol.

11. The method according to claim 8, characterized in that the regenerating gas is produced by mixing part of the exhaust gas regeneration with air or with air and nitrogen.

12. The method according to claim 8, characterized in that the stage of contacting the feedstock with a catalyst carried out in conjunction with additionally supplied registertask factions and/or oxygen-containing organic compounds.



 

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