RU2671568C1 - Complex installation for processing mixture of hydrocarbons c1-c10 of various composition and oxygen-containing compounds - Google Patents

Abstract

FIELD: technological processes.SUBSTANCE: present invention relates to a complex plant for processing a mixture of hydrocarbons C-Cdifferent compositions (low-octane gasoline fractions IBP – 180 °C, 90–160 °C or more narrow fractions, pentane-heptane (hexane) fractions, propane-butane fractions, WFLH – wide fractions of light hydrocarbons – a product of gas processing plants, and / or lower olefins C-Cand / or mixtures thereof with each other and / or with paraffins C-C, and / or with hydrogen) in the presence of oxygen-containing compounds, comprising one or more parallel sectioned adiabatic reactors consisting of one or more fixed beds (sections) of a zeolite-containing catalyst with heat input or removal between the catalyst beds (sections) or one or more isothermally co-located heat-pipe reactors in parallel, and / or coiled tubing and / or heat exchanger tubes and / or panels with heat input or output with a zeolite-containing catalyst, which can be fed to the feed mixture, as well as in the second and each subsequent layer (section) with the zeolite-containing catalyst in the adiabatic reactor, a part of the gas heated in the fire or electric heater, separated in the three-phase separator from the reaction products stream after their partial condensation, for the purpose of circulating it through a catalyst for supply or removal of heat in an adiabatic reactor, conversion of unsaturated hydrocarbons contained therein, and an increase in the regeneration range of the catalyst, technologically connected with the reactor heating, heat-exchange, separating, capacitive and pressure equipment for heating of raw materials, cooling, partial condensation, separation and rectification of reaction products. In addition, isobutane is also used as the feed stream, which preheated can be supplied alone and / or in admixture with oxygen-containing compounds C-Cand / or in admixture with an olefin-containing feedstock containing olefins C-C, as an input to the reaction part of the isothermal reactor or to the first layer (section) of the adiabatic reactor, and to the second and / or each subsequent layer (section) of the adiabatic reactor.EFFECT: proposed installation allows a simple way to obtain high octane gasolines, diesel fractions or aromatic hydrocarbons.11 cl, 3 dwg, 5 ex

Description

The invention relates to complex installations for the implementation of catalytic processes for the processing of C ₁ -C ₁₀ hydrocarbons of various compositions, including olefin-containing fractions, and oxygen-containing compounds C ₁ -C ₆ (organic monohydric alcohols and / or their ethers), in particular, to obtain high-octane gasoline from low-octane gasoline and / or olefin-containing fractions and methanol, diesel fractions from olefin-containing compounds and methanol or dimethyl ether, as well as to produce aromatic hydrocarbons and paraffin - or olefin containing raw material and methanol or other alcohols or esters thereof.

The development by Mobil Oil (USA) in the 1970s of catalysts based on zeolites of the pentasil group (types ZSM-5, ZSM-11 and others), active and stable in the reactions of dehydrocyclooligomerization of aliphatic hydrocarbons and the conversion of oxygenates to hydrocarbons, gave rise to rapid the development of this direction. A number of methods are known for producing high-octane gasolines and aromatic hydrocarbons from hydrocarbon fractions and / or alcohols and their ethers. Technology features are associated with high thermal effects of these processes: exothermic - in the conversion of oxygenates or olefin fractions to gasoline hydrocarbons, endothermic - in the dehydrocyclo-oligomerization or dehydrocyclization of paraffin hydrocarbons. The methods for producing high-octane gasolines from aliphatic hydrocarbons and oxygenates and complex devices for their implementation solve the problems of supplying the heat necessary for chemical reactions to the reactor and removing heat from the reactor, optimizing the conditions in the reaction zone, and simplicity and reliability of the process.

The processes of producing aromatic hydrocarbons and high-octane gasoline in the joint processing of hydrocarbon fractions and methanol occupy a special position. In this case, the catalytic process does not have a high thermal effect, since exothermic and endothermic reactions occur simultaneously and, in principle, a heat-balanced process is possible. In this case, technical solutions for processes using one type of raw material and high thermal effect of its conversion, for example, the use of tubular reactors with catalyst loading into pipes (RU 2069227, RU 2098173) or into the annulus (RU 65045, RU 2429910), or a cascade of reactors with the ability to control the temperature in each reactor during the heat exchange of intermediate streams in external heat exchangers or when cold streams of raw materials and circulating coolants are introduced are redundant in the joint processing of hydrocarbon fractions and methanol, lead to a complication of the process and high capital and operating costs.

Thus, the method and system for the conversion of methanol to gasoline according to US Pat. No. 5,602,289 involves the conversion of raw materials in more than two contact zones with a catalyst (a series of series reactors, five in the example), the volume of which is limited by the requirement of an adiabatic temperature increase in the zone of not more than 50 ° C , with the introduction into each layer of fresh raw materials and a diluent, hydrocarbons are not heavier than C ₅ .

In the method of producing hydrocarbons from aliphatic alcohols using several separate contact zones of the feedstock with the catalyst of US Pat. No. 4,542,252, temperature is controlled by cooling the reaction stream before entering each subsequent zone using an integrated heat exchanger.

At least two reaction zones with intermediate heat exchange of the intermediate reaction stream between the zones provides a method for producing high-octane gasoline fractions from hydrocarbon feed boiling up to 250 ° C and / or oxygen-containing organic compounds according to the method of RU 2208624. Hydrocarbon is separated from the product stream by the separation and rectification method gases, gasoline fraction and / or aromatic hydrocarbons, as well as heavy fraction, boiling above 180-215 ° C.

In the method for the joint processing of low-octane hydrocarbon fractions and aliphatic alcohols and / or dimethyl ether according to RU 2429910, an isothermal reactor with heat pipes is used, which allows the raw materials to come into contact with the catalyst under optimal conditions, but has all the disadvantages of a tubular reactor, including the difficulty of loading the catalyst , which is especially undesirable with a relatively short catalyst life.

A close to isothermal conversion of raw materials can be obtained in the method of converting methanol to olefins or gasoline according to the method of US 5191142 in a homogeneous reaction mixture, which is a mixture of methanol and olefin in a reactor with a fluidized bed of the catalyst or in a reactor with a stationary layer with back mixing.

The installation for the catalytic production of high-octane gasoline fractions and aromatic hydrocarbons according to the patent RU 2098173 includes a reactor block with a shell-and-tube type reactor, the catalyst is loaded into the tubes, and a gas coolant with a predetermined temperature, which is obtained by mixing air with flue gases generated in the heat generator, is fed into the annulus when burning fuel gas. The coolant after the reactor is used to heat the feed streams in a tubular heat exchanger before being fed into the tubular reactor. The installation includes two reactor units operating alternately, as well as technologically connected separators, distillation columns, heat exchange, capacitive, and pumping equipment.

The complex installation for producing high-octane gasoline from gasoline fractions and methanol according to RU patent No. 138334 (prototype) includes reactors, heating, heat exchange, separation, capacitive and discharge equipment for heating raw materials, cooling, partial condensation, separation and rectification reaction products, characterized in that each reactor includes at least two stationary catalyst beds, with the possibility of feeding into the raw material mixture, as well as in the second and each subsequent layer of heat in the fire heater part of the gas released in the three-phase separator from the stream of reaction products after their partial condensation.

Our complex plant for processing a mixture of hydrocarbons C ₁ C _{10 of} various compositions, including olefin-containing fractions, and oxygen-containing compounds C ₁ -C ₆ (organic monohydric alcohols and / or their ethers), in particular, to produce high-octane gasoline from low-octane gasoline and / or olefin-containing fractions and methanol, combines well-known approaches to solve the technical problem of ensuring the preferred temperature in reactors and can be used for simple and reliable real tion process for producing high octane components of gasoline, for example, US Patent 5019663, RU 2103322 and RU 2372988.

The complex installation of the present invention is intended for processing a mixture of C ₁ -C ₁₀ hydrocarbons of various compositions (low-octane gasoline fractions NK - 180 ° C, 90-160 ° C or narrower fractions, pentane - heptane (hexane) fractions, propane - butane fractions, BFLH - broad fractions of light hydrocarbons - a product of gas processing plants, and / or lower olefins C ₂ -C ₁₀ and / or mixtures thereof with each other and / or with paraffins C ₁ -C ₁₀ and / or with hydrogen) in the presence of oxygen-containing compounds (C ₁ -C ₆ alcohols and / or their ethers), including I am one or more parallel-mounted partitioned adiabatic reactors, consisting of one or more stationary layers (sections) of a zeolite-containing catalyst with heat supply or removal between the catalyst layers (sections), or one or more parallel isothermal reactors with heat pipes, and / or coils and / or pipe heat exchangers and / or panels with heat supply or removal with a zeolite-containing catalyst with the possibility of feeding into the raw material mixture, as well as into the second and each the next layer (section) with a zeolite-containing catalyst in an adiabatic reactor of a part of the gas (H ₂ and C ₁ -C ₄ hydrocarbons) heated in a fire or electric heater, separated from the reaction product stream in a three-phase separator after partial condensation, with a view to circulating it through the catalyst for supply or removal of heat in an adiabatic reactor, conversion of unsaturated hydrocarbons contained therein and increase in the inter-regeneration path of the catalyst, heating, heat exchange, vaporizing, capacitive and discharge equipment for heating the raw materials, cooling, partial condensation, separation and rectification of the reaction products, while isobutane is also used as the feed stream, which can be fed preheated alone and / or in a mixture with oxygen-containing compounds C ₁ -C ₆ and / or in a mixture with an olefin-containing raw material containing C ₂ -C ₁₀ olefins, both at the entrance to the reaction part of the isothermal reactor or to the first layer (section) of the adiabatic reactor, and to the second and / or each subsequent layer (section) of the adiabatic reactor.

The installation is characterized in that it includes a unit consisting of at least one reactor for removing sulfur compounds using a hydrogen-containing gas obtained in the process from at least part of the hydrocarbon feed C ₁ -C ₁₀ , into which the heated feed is directed, a stream purified from sulfur of the raw material and direct it to the raw material heater of the isothermal reactor or the first layer (section) of the adiabatic reactor.

The installation is characterized in that it includes a distillation column for the separation of C ₅₊ components from hydrocarbon feedstock (BFLH) in the case of aromatization of this feedstock and a vapor-phase vapor stream containing C ₁ -C ₄ hydrocarbons is sent from the isothermal reactor or the first layer (section) of the adiabatic reactor top of the column after the allocation of reflux.

The installation is characterized in that a C ₅ -C ₆ or C ₅ -C ₇ fraction is isolated in a distillation column from NGL with a side stream and this fraction is sent to the aromatization reactor.

The installation is characterized in that it includes at least one adsorber filled with an adsorbent and selectively adsorbing C ₅₊ hydrocarbons, including aromatic hydrocarbons, into which a vapor-phase stream separated in a three-phase separator is directed from the product stream, and vapor-phase C ₅₊ - depleted hydrocarbons are removed a stream containing hydrogen and C ₁ -C ₄ hydrocarbons.

The installation is characterized in that the sectioned adiabatic reactor, consisting of two or more layers (sections) of the catalyst, has an increasing volume distribution of the catalyst over the layers (sections) of the catalyst, namely, 1: 2: 3: 4: 6, etc. d.

The installation is characterized in that it has a separate independent circulation circuit for the regeneration of a zeolite-containing catalyst with a circulation compressor, heat exchange of return flows, separation equipment, a fire or electric heater for circulation through the reactors of a nitrogen-air mixture with nitrogen and air recharge with a mixture flow rate of 60-1800 nm ³ / m ^{3 of} catalyst and blowing off regeneration gases.

The installation is characterized in that in order to increase the selectivity of the process for liquid products (aromatic hydrocarbons or diesel fraction), the zeolite-containing catalyst in the adiabatic reactor is fed into the feed mixture after the desulfurization reactor of the adiabatic or isothermal reactors, and also in the second and / or each subsequent layer (section) of the adiabatic reactor the purpose of their circulation through the catalyst is unreacted components of liquid raw materials heated in a fire or electric heater (non-aromatic hydrocarbons in the case of aromatization ii hydrocarbons C ₁ -C ₁₀₎ or nontarget liquid products (olefin-containing gasoline fraction in the case of a diesel fraction from the olefin containing raw material) isolated from the product stream of absorption methods, and / or adsorption and / or the extractive rectification (distillation) (in the first case ) or rectification (in the second case).

The installation is characterized in that for regulating the thermal regime of the synthesis process, a separate supply of hydrocarbon raw materials (isobutane, C ₁ -C ₁₀ paraffins, and / or C ₂ -C ₁₀ olefins) and oxygen-containing compounds as directly at the beginning of the layers (sections) of adiabatic and isothermal is provided reactors, and the height of each layer (section) of the adiabatic reactor through special switchgears.

The installation is characterized in that the processing of raw materials (hydrocarbons C ₁ -C ₁₀ , oxygen-containing compounds C ₁ -C ₆ and isobutane) is carried out in the presence of catalysts based on zeolites of the pentasil group (ZSM-5, ZSM-11 and others) at a temperature of 250 -600 ° C, a pressure of 0.1-10.0 MPa, a volumetric feed rate (for liquid feed) of 0.1-10 hours ^-1 .

The installation is characterized in that the process of processing raw materials (hydrocarbons C ₁ -C ₁₀ , oxygen-containing compounds C ₁ -C ₆ and isobutane) is carried out with the following volume ratio of components (% wt. By liquid feed): hydrocarbons C ₁ -C ₁₀ : oxygen-containing compounds C ₁ -C ₆ - 1: (0.01-10.0); hydrocarbons C ₁ -C ₁₀ : isobutane - 1: (0.01-5.0).

The raw material of the process is straight-run oil or gas condensate low-octane gasoline fractions, boiling preferably up to 180 ° С, propane - butane fractions, BFLH and / or olefin-containing fractions, as well as isobutane and oxygen-containing organic compounds (C ₁ -C ₆ alcohols or their ethers) , for example, methanol of any degree of purification, including methanol - raw or dimethyl ether.

An integrated installation for providing continuous processing of raw materials may include two or more reactors operating alternately in a reaction-regeneration cycle. Isothermal or shelf adiabatic reactors are used with switchgears between at least two catalyst beds for introducing circulating heat carrier gas. Known catalysts based on zeolites of the pentasil group (ZSM-5, ZSM-11, and others) can be used, namely, dehydrocyclization of paraffins, oligomerization of olefins, or the conversion of methanol or dimethyl ether to gasoline hydrocarbons in the presence of which at a temperature of 250-600 ° With a pressure of 0.1-10.0 MPa, a volumetric feed rate (for liquid feed) of 0.1-10 hour ^-1 , mainly gasoline hydrocarbons are formed from paraffin or olefin-containing raw materials, from alcohols or ethers, aromatic hydrocarbons - of aliphatic hydrocarbons and oxygen-containing raw materials, diesel fraction - from olefin-containing raw materials, as well as cracking, alkylation and isomerization of hydrocarbons. Catalysts prepared according to patents RU 2087191, RU 2098455, RU 2100075, RU 2133640, RU 2165293, RU 2169043, RU 2284343, RU 2440189, or EAPO patent 002139 can be used.

The nitrogen-air oxidative regeneration of the hydrocarbon feed conversion catalyst in the reactors provides a regeneration loop.

The installation includes technologically connected recuperation heat exchangers and a fire heater for heating raw materials, a recuperation heat exchanger and a fire heater of recycle supplied both to the inlet to the reactor through the raw material line or through its own line, and to the second and subsequent catalyst layers in the adiabatic reactor, as well as air and water coolers for condensing the product stream components, a three-phase separator to separate it from the uncondensed components, mainly hydrocarbons C ₁ and C _2, in discharge phase, containing traces of hydrocarbons and oxygenated compounds, and unstable liquid catalysate, which is stabilized in a distillation column to obtain a stable concentrate of high octane gasoline or aromatic hydrocarbons (preferably benzene - toluene - xylene fraction) or stable gasoline and diesel fraction. If necessary, the gasoline fraction or BTX fraction can be divided into aromatic and non-aromatic hydrocarbons by absorption and / or adsorption and / or extractive distillation (distillation) methods. In the case of the targeted production of the diesel fraction from the olefin-containing feedstock, the resulting gasoline olefin-containing fraction is recycled from the distillation column, and in the case of the targeted production of aromatic hydrocarbons, the resulting non-aromatic hydrocarbons are recycled after separation from aromatic hydrocarbons by absorption and / or adsorption and / or extractive methods rectification (distillation). After separation of non-aromatic and aromatic hydrocarbons, the latter can be separated in a separate distillation column into individual hydrocarbons (benzene, toluene, xylenes, ethylbenzene, C ₉ aromatics, naphthalene, etc.).

If the paraffin-containing raw material (propane - butane fraction) must be fully aromatized and it contains C ₅₊ components (BFLH), they are separated in a stabilization column. In this case, the installation additionally includes a distillation column and equipment necessary for its functioning: a raw material heater, a reboiler or an evaporator for heating the column cube, a refrigerator, as well as a reflux tank and a pump for supplying cold irrigation to the column. A hydrocarbon-containing C ₁ -C ₄ vapor phase stream from the top of the column after reflux is sent for processing.

If it is necessary to aromatize the pentane-hexane or pentane-heptane fraction, then the C ₅ -C ₆ or C ₅ -C ₇ fraction is isolated in side distillation column from NGL and the fraction is sent to the aromatization reactor.

If the feed is represented by separate fractions of saturated hydrocarbons and olefin-containing fractions, the latter can be fed separately to each layer (section) of the zeolite-containing catalyst in an adiabatic reactor. This also applies to the supply of isobutane and oxygen-containing compounds. Such a feed of raw materials in an adiabatic reactor makes it possible to obtain conditions for a chemical process close to isothermal. In a preferred case, the olefin-containing and oxygen-containing compounds are mixed with the paraffin-containing and isobutane-containing feed before each layer (section) to obtain a mixture of hydrocarbons, 30-40% by weight. which are olefins and oxygen-containing compounds.

For a more complete extraction of C ₅₊ hydrocarbons from gaseous C ₁ -C ₄ hydrocarbons separated in a three-phase separator, some of which are subsequently sent to mix with the feed hydrocarbon stream of the installation (after the desulfurization reactor), without the use of high pressure and deep cold, the installation can include at least one or more adsorbers - to ensure continuous cleaning of the vapor-phase stream extracted from the product stream (RU 2277527, RU 57278). For adsorption of C ₅₊ hydrocarbons from a mixture of C ₁ -C ₄ hydrocarbons, known adsorbents can be used: activated carbon, silica gel, zeolites. It is preferable to use activated carbon as an easily regenerated sorbent with a high adsorption capacity. Adsorption is carried out in conventional adsorbers. The conditions for the adsorption of C ₅₊ hydrocarbons depend on the properties of the sorbent used and, in the preferred case, coincide with the characteristics of the cleaned vapor-phase stream.

The vapor-phase stream from the separator, if necessary, is directed to an adsorber located after the compressor on the circulation line of gaseous reaction products, preferably without preliminary preparation, and a vapor-phase C ₅₊ hydrocarbon depleted stream containing hydrogen and C ₁ -C ₄ hydrocarbons is removed from the adsorber. The degree of extraction of C ₅₊ hydrocarbons from the vapor phase stream is preferably not lower than 95% for a complete adsorption cycle.

Especially necessary is a block for the adsorption of C ₅₊ hydrocarbons (primarily benzene and toluene) from C ₁ -C ₄ hydrocarbons during the processes for producing aromatic hydrocarbons.

The adsorbent saturated with C ₅₊ hydrocarbons is regenerated by raising the temperature in the adsorber while the adsorbent is purged with part of the C ₅₊ depleted hydrocarbon stream from another adsorber (stripping gas) or an inert gas from the side. Desorbed C ₅₊ hydrocarbons are separated from saturated stripping gas with a lower volume of non-condensable components than in the adsorption stream, and their condensation and separation can be carried out with less loss.

In the regeneration mode, the heated stripping gas is supplied to the adsorber — part of the depleted C ₅₊ hydrocarbon stream from another adsorber or an inert gas (for example, nitrogen) if there is only one adsorber in the circuit and the stripping gas saturated with C ₅₊ hydrocarbons is removed. To regenerate the adsorbent, the installation includes a heater for heating the stripping or inert gas and heat exchangers and coolers connected in series with the outlet from the adsorber for cooling and condensing C ₅₊ hydrocarbons from saturated stripping or inert gas, as well as a separator for separating the vapor-liquid mixture from which the liquid-phase stream is removed containing C ₅₊ hydrocarbons, which are sent to a distillation column to stabilize, and a vapor phase stream that is mixed with C-depleted hydrocarbons ₅₊ flow from another adsorber, or inert gas.

Adsorbers and adsorbent regeneration equipment form an adsorption block. The inlet stream is a C ₅₊ hydrocarbon vapor stream from a three-phase separator of the product stream from the reactors, the outlet stream is a vapor phase stream depleted in C ₅₊ hydrocarbons or an inert gas, and a liquid phase stream containing C ₅₊ hydrocarbons.

In the absence of the need to clean the vapor-phase stream from the three-phase separator from C ₅₊ hydrocarbons, part of this stream is blown into the fuel network on the line in front of the circulation compressor.

An unstable liquid product from a three-phase separator through heat exchangers, where it is heated by the heat of a stable product, enters the distillation column for stabilization. Vapors are removed from the top of the column, which are cooled and condensed in an air cooler and a water cooler, and then non-condensed gas is released in the separator, which is sent to the fuel network, and liquefied gas, part of which is pumped into the column as irrigation, and the balance part is removed from plants as a commercial product (in some cases, this gas is used as plant raw materials). The bottoms product of the column enters the reboiler, where light fractions are evaporated from it, which then enter the bottom plate of the column, and the stable liquid product (high-octane gasoline, aromatic hydrocarbon concentrate or diesel fraction in the case of oligomerization of olefin-containing raw materials - in this case, the gasoline olefin-containing fraction columns with a side shoulder strap and sent for recycling for further processing, not shown in the diagrams) it is cooled in the annular space of the heat exchanger and fed to ny storage (in case of high-octane gasoline) or to a further separation of aromatic and nonaromatic hydrocarbons (in the case of a concentrate of aromatic hydrocarbon) block by standard methods in their separation.

In the latter case, aromatic and non-aromatic hydrocarbons (usually not more than 1.0% by weight) are separated by absorption and / or adsorption and / or extractive distillation (distillation) methods (A. Sulimov D. Production of aromatic hydrocarbons from petroleum feedstocks. M. Chemistry, 1975, p. 36-72). The content of non-aromatic hydrocarbons in the aromatic composition after the separation unit does not exceed 1000 ppm. After the separation unit, aromatic hydrocarbons can be separated in a separate distillation column into individual hydrocarbons (benzene, toluene, xylenes, C ₉ aromatics, naphthalene, etc.), and liquid non-aromatic hydrocarbons are removed from the unit as a commodity.

In fig. 1 (with two shelf adiabatic reactors), 2 (with two isothermal reactors for conducting exothermic reactions) and 3 (with two isothermal reactors for carrying out endothermic reactions) are schematic diagrams of a complex installation for producing high-octane gasoline, diesel fraction or aromatic hydrocarbons from C hydrocarbons ₁ -C _{10 of} various composition, oxygen-containing compounds and isobutane. The installation includes the following devices: E-1, E-2 - raw materials tanks; H-1, H-2, H-3, H-4, H-5 - pumps; P-1, P-2, P-3 - furnaces; P-1, P-2 - reactors; T-1, T-2, T-3, T-4, T-5, T-6, T-7 - heat exchangers; PK-1, PK-2 - compressors; ХВ-1, ХВ-2, ХВ-3 - air coolers; X-1, X-2 - water coolers, C-1, C-2, C-3, C-4 - separators; RB - reboiler; K-1 distillation column. The diagrams do not show: desulfurization reactor; K-2-distillation column separation BFLU; a block for the adsorption of C ₅₊ hydrocarbons from C ₁ -C ₄ hydrocarbons; block separation of aromatic and non-aromatic hydrocarbons; K-3 - distillation column separation of aromatic hydrocarbons. The flows are indicated on the diagrams: I — a raw hydrocarbon fraction C ₁ -C ₁₀ , II — a raw oxygen-containing fraction C ₁ -C ₆ , III — a raw mix, IV — products of a catalytic process, V — a hydrogen-containing gas; VI - water condensate; VII - unstable gasoline; VIII - liquefied gas; IX - stable product (high-octane gasoline or olefin-containing gasoline or diesel olefin-containing fraction or aromatic hydrocarbon concentrate).

Installation works as follows. Raw materials - hydrocarbon feed fraction C ₁ -C ₁₀ I (straight-run or gas condensate gasoline fraction or olefin-containing fraction or pentane-hexane (heptane) fraction or propane - butane fraction or BFLH) and isobutane from the feed tank E-1 is received at the raw material pump Н -2, where the raw oxygen-containing fraction C ₁ -C ₆ II is supplied from the feed tank E-2 to the pump N-1. NGL can be preliminarily separated in a K-2 distillation column (not shown in the diagrams) into fractions C ₁ -C ₄ , C ₅ -C ₇ , C ₅ -C ₆ , C ₅₊ , C ₆₊ or C ₇₊ , and any of these fractions can be used as the plant feed. If necessary, the scheme may include a desulphurization reactor for a raw gasoline fraction, pentane - hexane (heptane), NGL, and also any fraction extracted from NGL using the hydrogen-containing gas obtained in the process. The raw material mixture passes through the tube space of the T-3 and T-1 heat exchangers, where it is heated by a gas-product stream coming from the R-1 or P-2 reactor operating in the synthesis mode. Next, the feed stream III is heated in the furnace P-1 to the required temperature for the onset of the reaction (250-510 ° C, depending on the raw materials used) and enters the reactor R-1 or P-2 operating in the synthesis mode. At the same time, gas heated in the recovery heat exchanger T-2 and furnace P-3 to 410-480 ° C is supplied to the first or each subsequent catalyst bed or between these layers in an adiabatic reactor, as well as to the inlet of the isothermal reactor, by a PK-1 circulation compressor. as well as hot recycle stream from K-1 (not shown in the diagrams). In the reactor, depending on the raw materials used, at a temperature of 250-510 ° C and a pressure of 0.1-10.0 MPa, a catalytic process for the conversion of raw materials is carried out. The product stream IV is withdrawn from the reactor, which sequentially passes the annulus of the heat exchangers T-1, T-2 and T-3, where it transfers heat to the feed stream and circulating gas, then the T-4 heat exchanger, where it gives heat to the unstable product stream, is then cooled to XB-1 air refrigerator to a temperature of 55 ° C and then with circulating water in an X-1 water refrigerator to a temperature of 35 ° C. Next, the gas-liquid mixture of products enters the three-phase separator C-1, where it is divided into gas stream V, water condensate VI and unstable liquid product VII.

The main part of the gas stream extracted in the three-phase separator enters the PK-1 circulation compressor unit at a pressure of 1.9-2.0 MPa (in the preferred case, when producing high-octane gasolines) and 4.0-6.0 (in the preferred case, when receiving diesel fractions from olefin-containing raw materials) enters the coil of the T-2 heat exchanger, then to the P-3 furnace and then to the R-1 or R-2 reactor operating in the synthesis mode.

Water condensate containing acidic components and unreacted alcohol (ether) (usually traces) is sent to a water treatment system or to an oil desalination plant.

The unstable product VII (gasoline, aromatic hydrocarbon concentrate or diesel fraction) is pumped to the T-4 heat exchanger coil, then to the T-5 heat exchanger coil, where it is heated by the heat of a stable product, and then goes to stabilization in the K- distillation column one. Vapors are removed from the top of the column, which are cooled and condensed in the ХВ-2 air cooler and the Х-2 water cooler, and then non-condensed gas is released in the С-2 separator, which is sent to the fuel network, and liquefied gas, some of which is pumped by the Н-4 sent to the column as irrigation, and the balance part VIII is removed from the installation. The bottoms product of the column enters the RB reboiler, where light fractions are evaporated from it, which then go under the bottom plate of the column, and the stable product IX — high-octane gasoline or olefin-containing gasoline or diesel fraction — is cooled in the annular space of the T-5 heat exchanger and delivered to the warehouse . If the target stable product of the K-1 column is the diesel fraction obtained by oligomerization of olefin-containing raw materials, then the gasoline fraction obtained in the process is removed by the side stream of the K-1 column and sent for recycling to the P-1 or P-2 reactor (not shown in the diagrams )

If the stable product of the column is a concentrate of aromatic hydrocarbons in the case of aromatization of hydrocarbons, then further processing of this product occurs as follows.

Aromatic and non-aromatic (usually not more than 1.0 wt.%) Hydrocarbons are separated by absorption and / or adsorption and / or extractive distillation (distillation) methods. The content of non-aromatic hydrocarbons in the aromatic composition after the separation unit does not exceed 1000 ppm. After the separation unit, aromatic hydrocarbons can be separated in the K-3 distillation column into individual hydrocarbons (benzene, toluene, xylenes, C ₉ aromatics, naphthalene, etc.), and liquid non-aromatic hydrocarbons are removed from the unit as a commodity, as well as in some cases can be sent for recycling in the aromatization process.

As the coking of the catalyst in the synthesis reactor P-1 or P-2, the temperature of the incoming feed stream rises. After reaching the maximum processing temperature of each type of raw material, a reactor with a catalyst that has lost activity is disconnected from the feed stream and transferred to the oxidative regeneration mode with a nitrogen-air mixture through a regeneration circuit. The circuit for supplying nitrogen and air to the S-4 separator and the line of the nitrogen-air mixture from S-4 to receive the PK-2 circulation compressor are launched. At the beginning of regeneration, the reactor is purged from “combustible” compounds with pure nitrogen. Nitrogen after the circulation compressor PK-2, the tube space of the heat exchangers T-6 and T-7 through the P-2 furnace enters the reactor with a coked catalyst. After leaving the reactor, nitrogen, and subsequently the nitrogen-air mixture, passes the annular space of the T-7 and T-6 heat exchangers, where it gives off heat to the fresh nitrogen-air mixture. Next, nitrogen (nitrogen-air mixture) through the XB-3 refrigerator enters the C-3 separator, where part of it is blown off to the candle, and the other part through the C-4 separator again enters the regeneration circuit. After lowering the temperature in the reactor to 280 ° C and the content of "combustible" less than 0.5% vol. begin a gradual dosage of air (up to 100%) in nitrogen in the C-4 separator and a gradual increase in temperature in the P-2 furnace to 510 ° C. The duration of the regeneration cycle is up to 120 hours.

The invention can be illustrated by the following examples.

Example 1

According to the described technological scheme (Fig. 1) under conditions: temperature 380 ° C, pressure 0.8 MPa, volumetric feed rate (liquid) 1.5 hour ^-1 from 14800.0 kg / hour of gasoline fraction boiling out within 38-165 ° C, 200.0 kg / h of isobutane and 3750.0 kg / h of methanol in contact with the zeolite-containing catalyst in three zones of the adiabatic reactor at a temperature of exit from each zone only 4-5 ° C lower than the temperature at the inlet to the zone receives 14550.0 kg / h of stable gasoline with a benzene content of 0.85% wt. and an octane rating of 94 points according to the research method, 1391.0 kg / h of C ₃ -C ₄ fraction, 2109.4 kg / h of water condensate and 699.6 kg / h of gas purge sent to the fuel network.

Example 2

According to the described technological scheme (Fig. 1) under conditions: temperature 300 ° C, pressure 1.8 MPa, bulk feed rate (by liquid) 2 hours ^-1 from 14,600.0 kg / h of butane - butylene fraction (composition,% wt .: propane - 1.0; propylene - 1.0; isobutane - 8.0; n-butane - 28.0; butenes - 62.0; total olefins - 63.0), 400.0 kg / hour of isobutane and 3750.0 kg / hr of dimethyl ether in contact with a zeolite-containing catalyst in four zones of an adiabatic reactor at a temperature at the outlet of each zone only 5-8 ° C above the temperature at the entrance to the zone, 12020.0 kg / hr of stable gasoline are obtained with benzene content of less than 0.1% wt. and an octane number of 97.5 points according to the research method, 3427.0 kg / h of fraction C ₃ -C ₄ , 1467.4 kg / h of water condensate and 1835.6 kg / h of gas purge directed to the fuel network.

Example 3

According to the described technological scheme (Fig. 2) under conditions: temperature 260 ° C, pressure 4.2 MPa, bulk feed rate (by liquid) 1 hour ^-1 from 14,900.0 kg / h of propane - propylene fraction (composition,% wt .: propane - 30.0, propylene - 70.0), 100.0 kg / h of isobutane and 3750.0 kg / h of a mixture of methanol and dimethyl ether (1: 1 by weight) in contact with a zeolite-containing catalyst in an isothermal reactor with heat removal from the reaction space at a temperature at the outlet of the reactor only 2-3 ° C above the temperature at the inlet of the reactor, 12480.0 kg / h of diesel fraction are obtained and (170-270 ° C) with a cetane number of 34.0 (before hydrotreating) and 53.0 (after hydrotreating), 3350.0 kg / h of gasoline fraction (38-170 ° C), 920.0 kg / h of fraction C ₃ -C ₄ , 1790.4 kg / h of water condensate and 209.6 kg / h of gas purge sent to the fuel network.

Since in this example, the target stable product of the K-1 column is the diesel fraction obtained by oligomerization of an olefin-containing raw material (propane - propylene fraction), the gasoline fraction formed in the process is removed by the side stream of the K-1 column and, after heating, is sent for recycling to the reactor P-1 or P-2 (not shown in the diagram).

Example 4

According to the described technological scheme (Fig. 3) under conditions: temperature 520 ° C, pressure 0.8 MPa, bulk feed rate (liquid) 1 hour ^-1 from 11000.0 kg / h of propane-butane fraction (composition,% wt .: propane - 50.0, butane - 50.0), 3000.0 kg / h of isobutane and 4750.0 kg / h of a mixture of alcohols C ₂ -C ₄ (ethanol: isopropanol: butanol - 1: 1: 1 each mass) upon contact with a zeolite-containing catalyst in an isothermal reactor with heat supplied to the reaction space at a temperature at the outlet of the reactor only 3-4 ° C lower than the temperature at the inlet of the reactor, 11,550.0 kg / hour of concentrate are obtained aromatic hydrocarbons, 320.0 kg / h of the C ₃ -C ₄ fraction, 1425.0 kg / h of water condensate and 5455.0 kg / h of gas purge directed to the fuel network.

Since the target product of this example is a concentrate of aromatic hydrocarbons, the typical scheme (Fig. 3) is finalized as follows.

The vapor-phase flow from the C-1 three-phase separator is directed to an adsorber located after the compressor on the circulation line of the gaseous reaction products. From the adsorber, a vapor-phase stream containing hydrogen and C ₁ -C ₄ hydrocarbons depleted in C ₅₊ hydrocarbons depleted of hydrocarbons (mainly aromatic hydrocarbons, in particular benzene and toluene) is recycled to the P-1 or P-2 reactor. The degree of extraction of C ₅₊ hydrocarbons from the vapor phase stream is preferably not lower than 95% for a complete adsorption cycle.

Aromatic and non-aromatic (usually not more than 1.0% by weight) hydrocarbons (stream IX from column K-1) are separated by absorption and / or adsorption and / or extractive distillation (distillation) methods in the separation unit for aromatic and non-aromatic hydrocarbons ( not shown). The content of non-aromatic hydrocarbons in the aromatic composition after the separation unit does not exceed 1000 ppm. After the separation unit, aromatic hydrocarbons can be separated in a K-3 distillation column (not shown in the diagram) into individual hydrocarbons (benzene, toluene, xylenes, C ₉ aromatics, naphthalene, etc.), and liquid non-aromatic hydrocarbons are removed from the unit as product.

In this example, from the resulting 11550.0 kg / h of aromatic hydrocarbon concentrate in the K-3 column, it is possible to obtain (% wt.): Benzene 20-24; toluene 32-34; the amount of xylenes 24-27; ethylbenzene 2-3; aromatics C ₉ 3-4; naphthalene 5-7; methylnaphthalenes 5-7; the rest is 1.

Example 5

According to the described technological scheme (Fig. 3) under conditions: temperature 500 ° C, pressure 0.5 MPa, bulk feed rate (by liquid) 2 hours ^-1 from 14500.0 kg / hour of pentane - hexane fraction (composition,% wt .: pentane - 50.0, hexane - 50.0) isolated from BFLH, 500.0 kg / h of isobutane and 3750.0 kg / h of methanol in contact with a zeolite-containing catalyst in an isothermal reactor with heat being introduced into the reaction space at temperature at the outlet of the reactor only 2-3 ° C below the temperature at the inlet of the reactor receive 12300.0 kg / h of aromatic hydrocarbon concentrate , 1100.0 kg / h of fraction C ₃ -C ₄ , 2109.4 kg / h of water condensate and 3240.6 kg / h of gas purge directed to the fuel network.

Since the raw material of this example is NGL, and the target product of the process is a concentrate of aromatic hydrocarbons, the typical scheme (Fig. 3) is finalized as follows.

If BFLH contains sulfur compounds, the installation includes a unit consisting of at least one reactor to remove sulfur compounds using the hydrogen-containing gas obtained in the process from at least part of the C ₁ -C ₁₀ hydrocarbon feed to which the heated feed is sent from the reactor removes the stream of sulfur-free raw materials and directs it to the raw material heater of the isothermal reactor. In this case, it is preferable to purify the entire BFLH stream so that all further products of BFLH processing that are formed in the future will be purified from sulfur.

The pentane-hexane fraction, which must be completely aromatized, is isolated by side stream in a K-2 distillation column (not shown in the diagram) and this fraction is sent to the aromatization reactor.

Purification of the exhaust gas from the reactor and purification and separation of the resulting aromatic hydrocarbons is carried out as in example 4.

The vapor-phase flow from the C-1 three-phase separator is directed to an adsorber located after the compressor on the circulation line of the gaseous reaction products. From the adsorber, a vapor-phase stream containing hydrogen and C ₁ -C ₄ hydrocarbons depleted in C ₅₊ hydrocarbons depleted of hydrocarbons (mainly aromatic hydrocarbons, in particular benzene and toluene) is recycled to the P-1 or P-2 reactor. The degree of extraction of C ₅₊ hydrocarbons from the vapor phase stream is preferably not lower than 95% for a complete adsorption cycle.

Aromatic and non-aromatic (usually not more than 1.0% by weight) hydrocarbons (stream IX from column K-1) are separated by absorption and / or adsorption and / or extractive distillation (distillation) methods in the separation unit for aromatic and non-aromatic hydrocarbons ( not shown). The content of non-aromatic hydrocarbons in the aromatic composition after the separation unit does not exceed 1000 ppm. After the separation unit, aromatic hydrocarbons can be separated in a K-3 distillation column (not shown in the diagram) into individual hydrocarbons (benzene, toluene, xylenes, C ₉ aromatics, naphthalene, etc.), and liquid non-aromatic hydrocarbons are removed from the unit as product.

In this example, from the resulting 12300.0 kg / h of aromatic hydrocarbon concentrate in the K-3 column, it is possible to obtain (% wt.): Benzene 18-25; toluene 30-40; the amount of xylenes 14-22; ethylbenzene 1-2; aromatics C ₉ 4-5; naphthalene 2-5; methylnaphthalenes 3-6; the rest is 1.

Claims (11)

1. Complex installation for processing a mixture of C ₁ -C ₁₀ hydrocarbons of various compositions (low-octane gasoline fractions, NK - 180 ° C, 90-160 ° C or narrower fractions, pentane-heptane (hexane) fractions, propane-butane fractions , NGL - broad fractions of light hydrocarbons - product of gas processing plants, and / or lower olefins C ₂ -C ₁₀ and / or mixtures thereof with each other, and / or with C ₁ -C ₁₀ paraffins, and / or with hydrogen) in the presence of oxygen-containing compounds (alcohols C ₁ -C ₆ and / or their ethers), including one or more parallel located sectionalized adiabatic reactors consisting of one or more stationary layers (sections) of a zeolite-containing catalyst with heat supply or removal between the layers (sections) of the catalyst, or one or more parallel isothermal reactors with heat pipes, and / or coils, and / or pipe heat exchangers, and / or panels with heat supply or removal with a zeolite-containing catalyst with the possibility of feeding into the raw material mixture, as well as into the second and each subsequent layer (section) with a zeolite-containing m the catalyst in the adiabatic reactor is heated in the combustion part of a gas or electric heater (H ₂ and hydrocarbons C ₁ -C ₄₎ selected in the three-phase separator from the reaction product fluid after partial condensation, with a view to its circulation through the catalyst for the supply or removal of heat in an adiabatic the reactor, the conversion of unsaturated hydrocarbons contained therein and the increase in the inter-regeneration path of the catalyst, heating, heat exchange, separating, capacitive and discharge technologically connected with the reactor equipment for heating raw materials, cooling, partial condensation, separation and rectification of reaction products, while isobutane is also used as a feed stream, which can be fed preheated alone and / or in a mixture with oxygen-containing compounds C ₁ -C ₆ and / or in a mixture with an olefin-containing raw material containing C ₂ -C ₁₀ olefins, both at the entrance to the reaction part of the isothermal reactor or to the first layer (section) of the adiabatic reactor, and to the second and / or each subsequent layer (section) adiabatically oh reactor. 2. Installation according to claim 1, characterized in that it includes a unit consisting of at least one reactor for removing sulfur compounds using a hydrogen-containing gas obtained in the process from at least part of the C ₁ -C ₁₀ hydrocarbon feed, into which the heated feed is sent , a stream of sulfur-free raw material is removed from the reactor and directed to a raw material heater of the isothermal reactor or the first layer (section) of the adiabatic reactor. 3. Installation according to claim 1, characterized in that it includes a distillation column for separating C ₅₊ components from hydrocarbon feed (BFLH) in case of aromatization of this feed and the hydrocarbon containing C is sent to the feed of the feed from the isothermal reactor or the first layer (section) of the adiabatic reactor ₁ -C ₄ vapor phase flow from the top of the column after the allocation of reflux. 4. Installation according to claim 3, characterized in that in the distillation column from NGL side fraction C ₅ -C ₆ or C ₅ -C _{7 is} isolated in a side stream and this fraction is sent to the aromatization reactor. 5. Installation according to claim 1, characterized in that it includes at least one adsorber filled with an adsorbent and selectively adsorbing C ₅₊ hydrocarbons, including aromatic hydrocarbons, into which the vapor-phase stream separated in the three-phase separator from the product stream is directed and removed depleted C ₅₊ - hydrocarbons vapor-phase stream containing hydrogen and C ₁ -C ₄ hydrocarbons. 6. Installation according to claim 1, characterized in that the sectioned adiabatic reactor, consisting of two or more layers (sections) of the catalyst, has an increase in the layers (sections) from the first to the last volume distribution of the catalyst, namely 1: 2: 3: 4: 6 and so on. 7. Installation according to claim 1, characterized in that it has a separate independent circulation circuit for regenerating a zeolite-containing catalyst with a circulation compressor, heat exchange of return flows, separation equipment, a fire or electric heater for circulation through the reactors of a nitrogen-air mixture with nitrogen and air recharge with a flow rate mixtures of 60-1800 nm ³ / m ^{3 of} catalyst and by blowing off regeneration gases. 8. Installation according to paragraphs. 1, 2, characterized in that to increase the selectivity of the process for liquid products (aromatic hydrocarbons or diesel fraction) in the feed mixture after the desulfurization reactor of an adiabatic or isothermal reactor, as well as in the second and / or each subsequent layer (section) of a zeolite-containing catalyst in an adiabatic the reactor is fed with the aim of circulating through the catalyst unreacted components of liquid raw materials heated in a fire or electric heater (non-aromatic hydrocarbons in the case of aromatization process hydrocarbons) or non-target liquid products (olefin-containing gasoline fraction in the case of obtaining a diesel fraction from olefin-containing raw materials) isolated from the product stream by absorption, and / or adsorption, and / or extractive distillation (distillation) (in the first case), or rectification (in second case). 9. Installation according to claim 1, characterized in that for regulating the thermal regime of the synthesis process, a separate supply of hydrocarbon feeds (isobutane, C ₁ -C ₁₀ paraffins and / or C ₂ -C ₁₀ olefins) and oxygen-containing compounds as directly at the beginning of the layers is provided (sections) of the adiabatic and isothermal reactors, and the height of each layer (section) of the adiabatic reactor through special switchgears. 10. Installation according to claim 1, characterized in that the processing of raw materials (hydrocarbons C ₁ -C ₁₀ , oxygen-containing compounds C ₁ -C ₆ and isobutane) is carried out in the presence of catalysts based on zeolites of the pentasil group (type ZSM-5, ZSM- 11 and others) at a temperature of 250-600 ° C, a pressure of 0.1-10.0 MPa, a volumetric feed rate (for liquid feed) of 0.1-10 h ^-1 . 11. Installation according to claim 1, characterized in that the process of processing raw materials (hydrocarbons C ₁ -C ₁₀ , oxygen-containing compounds C ₁ -C ₆ and isobutane) is carried out in the following volume ratio of components (% wt. By liquid feed): hydrocarbons C ₁ -C ₁₀ : oxygen-containing compounds C ₁ -C ₆ - 1: (0.01-10.0); hydrocarbons C ₁ -C ₁₀ : isobutane - 1: (0.01-5.0).

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