The method of obtaining aromatic hydrocarbons from petroleum gas

 

(57) Abstract:

Describes the method of obtaining aromatic hydrocarbons from petroleum gas by the reaction of dehydrocyclization components3+raw materials for zeolite catalysts, in which the stream leaving the reaction zone and containing hydrogen, alkanes WITH1-C4and aromatic hydrocarbons WITH6+served in the separation zone, the separation zone output vapor stream containing hydrogen and methane, and liquid-phase I process flow containing propane, butane and aromatic hydrocarbons WITH6+served I the process flow in the fractionation zone and divide it into at least a second process flow containing propane and butane, and the first product stream containing aromatic hydrocarbons WITH6+serving II process flow in the reaction zone of dehydrocyclization, working in conditions of dehydrocyclization, and receive the stream leaving the reaction zone, wherein the vapor stream from the separation zone also contains ethane, and in the reaction zone is served raw materials containing alkanes WITH1-C4and part of the vapor stream from the separation zone. The technical result - the simplification and efficiency of the process technology. 2 C.p. f-crystals, 4 Il, 8 PL.

Associated petroleum gases produced from oil due to the pressure drop when lifting the oil to the wellbore to the surface or form a gas cap of an oil field. 1 ton of crude oil produced in an average 95-112 m3gas /Ed. S. K. Gardeners. The reference oil.- L.: Chemistry, 197 8, S. 48/. Associated gas is separated from the oil by the method of separation and sent for processing to a processing plant. The gas is dry and cleaned from sulphur, remove unstable gasoline is a hydrocarbon, C3+and the stripped gas is compressed and pumped to consumers. Unstable gasoline is separated into liquefied natural gas or individual hydrocarbon, C3and C4and stable gasoline. Receiving from petroleum gas liquefied propane-butane fuel /household or car/ often irrational, because in most regions of Russia there is no appropriate infrastructure and implementation of the product difficult.

Part of the produced associated gas has a low pressure, the cost of its kompremirovannyj and transport on GPP are great, and burn it on the torches, which leads to loss of hydrocarbon sii associated gas to produce salable products, with the increased demand.

In the patent literature describes numerous zeolite catalysts for the conversion of light aliphatic hydrocarbons to aromatics. The closest to implementation is the process "Cycler", developed jointly by the companies "UOP" and "British petroleum" /A. H. Dorogochinskii and other low molecular paraffin Aromatization of hydrocarbons on zeolite catalysts. Survey information. -M, Tsniiteneftehim, 1989, vol. 4/. It is used to convert liquefied gases or their mixtures with 10-50% of ethane to aromatic hydrocarbons and hydrogen. When using athenagorase raw material the process is carried out under more severe conditions, however, reach a minor conversion of ethane.

Of the products extracted aromatic hydrocarbons, hydrogen, neprevyshenie propane and butane /recycling/ and fuel gas through a complex system of separation. So, /SU 1523052 A3, 1989/ described method of separating the reaction products steam dehydrocyclization hydrocarbon, C3and C4that is carried out in four zones vapor-liquid separation using absorber, stripper and two distillation columns.

The closest technical is one gas, containing nitrogen, methane, ethane, propane and butane. The method includes compression and flow out of the reaction zone of dehydrocyclization stream containing hydrogen, ethane, propane, and aromatic hydrocarbon, C6+in the area of the liquid-vapor separation operated at conditions including a pressure of 2.8 MPa/, effective for the separation of incoming components for vapor exhaust stream containing nitrogen, hydrogen and methane, and liquid-phase I process flow containing ethane, propane, and aromatic hydrocarbon, C6+feeding raw natural gas into a zone of vapor-liquid separation; feeding the first flow of process in the fractionation zone containing at least one distillation column operated at conditions effective to separate the hydrocarbons of the first flow of process on at least a second process flow containing propane, and the first product stream containing hydrocarbons, C6+and the removal of this stream from the process; filing II flow process in the area of dehydrocyclization, working in conditions of dehydrocyclization, including at a pressure of less than 0.7 MPa, and producing a stream leaving the reaction zone.

In the described method, the raw materials into the reaction zone of dehydrocyclization, OTDELENIE or deep cold. In a preferred embodiment, the fractionation zone consists of several fractionation columns for separation of ethane and propane-butane fraction, which is the raw material for the reaction zone. However, this can be raw and light hydrocarbons, C2-C4isolated from the first flow of process in a single fractionation column II as the flow of the process.

The aim of the invention is to provide a simple and cost-effective technology for the processing of associated gas with obtaining a concentrate of aromatic hydrocarbons, dry gas and, if necessary, liquefied gas.

In the proposed methods of processing of associated gas in the reaction zone of dehydrocyclization serves non-condensable components and hydrocarbon, C2-C4raw materials and recycle streams. Nitrogen, methane and ethane are coolants, providing an endothermic conversion of propane and butane, which allows the reaction dehydrocyclization raw materials in single-stage adiabatic reactor without intermediate heating partially converted feedstock, complicating the design of the reactor and furnace.

In the inventive method for obtaining aromatic hydrocarbons from petroleum gas at reaky reaction and containing hydrogen, alkanes C1-C4and aromatic hydrocarbon, C6+served in the separation zone, the separation zone output vapor stream containing hydrogen, methane and ethane and 1 process flow containing propane, butane and aromatic hydrocarbons, C6+served I the process flow in the fractionation zone and divide it by at least II process flow containing propane and butane, and the first product stream containing aromatic hydrocarbons, C6+serves part of the vapor stream from the separation zone, the second flow of the process and raw materials containing alkanes C1-C4in the reaction zone of dehydrocyclization, working in conditions of dehydrocyclization, and receive the stream leaving the reaction zone.

The inventive method for processing hydrocarbons differs from the prototype the following characteristics: vapor stream is allocated in the zone of separation, also contains ethane in the reaction zone serves a portion of the vapor stream from the separation zone and raw materials containing alkanes C1-C4.

The raw material used or associated gas, containing 20-30 wt.%. /usually 30-50% wt./ hydrocarbon, C3+or associated gas and light hydrocarbon fraction, enriched with C5+: condensates, widelyused hydrocarbon, C5+-fractions of light hydrocarbons and/or gas in the reaction zone of dehydrocyclization direct hydrocarbon, C1-C4and non-condensable components, made of raw materials.

In the proposed methods of processing natural gas to carry out the catalytic dehydrocyclization components C3+raw materials with the formation of aromatic hydrocarbons, C6+and hydrogen. In the process form methane and ethane as by-products because of the low selectivity of the known catalysts dehydrocyclization. In liquid products also contain nonaromatic hydrocarbons, C5+their number depends on the catalyst and the process conditions and in the best case is reduced to less than 0.1% wt. In the stream leaving the reaction zone, also contain inert components of the feedstock and recycle used as heat transfer fluids, and neprevyshenie propane and butane, which emit in the fractionation zone and partially in the zone of separation and return to the reaction zone.

The reaction zone includes a variety of equipment necessary for implementation of the contact of the feedstock with the catalyst digitalkameras in terms of dehydrocyclization. This recuperaciones known highly selective composition of the zeolite group of pentelow and metal promoters, increasing activity, stability and selectivity of zeolites.

Conditions dehydrocyclization is normal for zeolite catalysts dehydrocyclization: the temperature of 500-550oC, a pressure of not more than 3 MPa, the volumetric feed rate of 0.5 - 6.0 hours-1.

The area of separation of flow coming from the reaction zone, provides for the separation of the vapor stream, containing mainly methane and ethane, and liquid-phase stream /I flow process/ containing mainly hydrocarbons, C3+. For this purpose, the stream exiting the reactor, cooled, condensed components C3+and carry out vapor-liquid separation flow, or absorb the components of C3+part I of the product stream from the fractionation zone, or use a combination of methods for vapor-liquid separation of the partially condensed stream and absorption components of the vapor stream for redistribution components of C3and C4in the streams of light hydrocarbons released into the separation zone and in the zone of the fractionation.

When using the absorption method for separation of components of C3+from the stream exiting the reactor, the first process thread also contains absorbent - part I-flow products the program flow, emerging from the reaction zone, the separator /separator/ and/or absorption column. Conditions of the liquid-vapor separation determine the content of propane and butane in the vapor stream and can be very hard, because recycling the vapor flow reduces the potential loss of raw materials process dehydrocyclization.

The fractionation zone comprises at least one fractionation column and provides the selection of the target product of the process - aromatic hydrocarbons, C6+or high-octane gasoline, resulting in stabilization of the mixture of the first process flow containing hydrocarbons, C3+and feedstock enriched in hydrocarbons, C5+. In the fractionation zone, if necessary, get a second product of the process - propane-butane fraction and/or the second recycle stream enriched in propane and butane.

Raw material containing a hydrocarbon, C5+/condensates and/or associated gas/ if the conversion in the reaction zone is undesirable sent to the fractionation zone and separated from him alkanes C1-C4that is directed into the reaction zone. The fractionation of the mixture of the first stream of process and feedstock recirculating hydrocarbons emit in a single stream with alkaram realizowany on the following technological schemes.

In Fig. 1 shows a diagram of the processing of associated gas with obtaining a concentrate of aromatic hydrocarbons. Zone separation forms a cage with a heat exchange apparatus, the area of the fractionation stabilisation column with the appropriate equipment. Upon contact of the feedstock with the catalyst in the reactor 3 receive the stream III, which is cooled in unit heat exchanger 4, the heat exchanger 12, in air refrigerator 5 and the refrigerator 6 and fed into the separator 4, where the partially condensed stream emit vapor stream IV and part of his /stream V/ direct mixing with the raw material gas, and the carrying amount on the transport stream VI/. The liquid phase from the separator is a first process flow is heated in the heat exchanger 8 and is served in the stabilization column 9. From the top of the column output pairs VIII - hydrocarbon, C1-C4that is partially condensed by cooling in air refrigerator 10 and the condensate is used for irrigation columns /thread IX/, and pair - II process flow is away from the reflux tank 11 and is sent to the mixing with the raw material gas. From the bottom of the column output aromatic hydrocarbon, C6+/thread VII/ I product of the process. In the reactor are sent compressed by the compressor 1 and heated can be carried out by obtaining a concentrate of aromatic hydrocarbons and propane-butane fraction. In Fig. 2 is a flow diagram of such a variant implementation of the proposed method. The separation zone includes a separator, in which the liquid-vapor separation of the cooled and partially condensed stream emerging from the reactor, and an absorption column in which the vapor stream absorb hydrocarbons, C3+part of the product C6+highlighted in the fractionation zone. The rich absorbent is sent to a fractionation zone for separation of light components and products.

Stream III, coming out of the reactor 3 and the resulting contact of the feedstock with the catalyst, cooled in heat exchanger 12, in block heat exchangers 4, refrigerators 5 and 6, and fed into the separator 7, where the liquid-vapor separation of the flow. Vapour phase IV of the separator serves in the absorption column 13 and absorb the components of C3+. Dry gas V from the separator is directed to the mixing of raw materials /stream VII/ and compression for filing in the pipeline /flow VI/. Absorbent, enriched with C3+/thread XI/, in a mixture with a liquid-phase stream 1 is heated in the heat exchanger 8 and is served in the stabilization column 9. From the bottom of the column output aromatic hydrocarbon, C6+/photodiode - propane and butane mixed with methane and ethane /thread XII/, cool them in the air the refrigerator 10 and the condensed propane-butane fraction from the reflux tank 11 output as a second product of the process /thread XIII/. A pair of reflux tank is directed to the mixing of raw materials is a second process flow, recycling of the fractionation zone. A mixture of the original APG XV, recycling from the zone of separation VII, recycling from the fractionation zone II is compressed by the compressor 1 is heated in the heat transfer block 4 and the furnace 2, and fed into the reactor, where are dehydrocyclization raw components.

The proposed method can be recycled raw material containing a hydrocarbon, C5+. Usually associated gas contains 3-10% wt. hydrocarbon, C5+and can be recycled without topping. However, the presence in the raw materials of a significant number of components C5+in the harsh conditions of dehydrocyclization propane and butane may result in reduced stability of the catalyst. On the other hand, when the allocation of oil associated gas and its compression gain condensates and NGL containing propane, butane and hydrocarbon, C5+and their involvement in the processing with the aim of obtaining aromatic hydrocarbons as Vysokaya, enriched with C5+in the reaction zone of dehydrocyclization serves non-condensable components and hydrocarbon, C1-C4isolated from raw materials. Raw material containing a hydrocarbon, C5+served together with the first flow process in the fractionation zone and receive a second flow of the process containing recycled hydrocarbons from the first process flow, non-condensable components and alkanes C1-C4feedstock and product of the process is high - octane gasoline containing hydrocarbons, C5+raw materials and aromatic hydrocarbons, C6+obtained in the area of dehydrocyclization.

In Fig. 3 shows a diagram of the processing of associated gas and condensate containing alkanes C4-and gasoline hydrocarbons, C5+. In the reaction zone in accordance with the proposed method serves recycled hydrocarbons, raw associated gas and a hydrocarbon, C4-isolated from raw condensate fractionation zone.

Stream III, coming out of the reactor 4 and the resulting contact of the feedstock with the catalyst, cooled in heat exchanger 5, in block heat exchangers 2 and in the air the refrigerator 6 and fed into the absorber 7, where it absorb hydrocarbons which are in heat exchanger 8 and is served in the stabilization column 9. Pair with the top of the column /thread VIII/ containing mainly hydrocarbons, C1-C4cool in the air of the refrigerator 10 and the condensate is used as a cold irrigation IX, and pairs II of the reflux tank 11 serves for mixing with the raw material gas. The bottom product X contains aromatic hydrocarbon stream leaving the reactor and the hydrocarbon, C5+raw condensate and is a high-octane gasoline. Gasoline is cooled in heat exchanger 8 and air refrigerator 12, a part of his /absorbent XII/ use to get in the zone of separation of liquid-phase I of the process flow. Dry gas V of the absorber serves to mix with the raw materials /thread XIII/ and the carrying amount in the pipeline. In the reactor serves thread XVI - a mixture of raw associated gas XI, recycle stream XIII from the zone of separation and the mixture of recycle and components C4-raw condensate from the fractionation zone /stream II/.

In Fig. 4 shows a diagram of the processing of associated gas, enriched hydrocarbon, C5+and unstable condensate gasoline hydrocarbons. In the reaction zone of dehydrocyclization serves recycle stream from the separation zone and a mixture of recycled hydrocarbons, recondenser the e fractionation. In the fractionation zone there is also the first product of the process - stable high-octane gasoline containing hydrocarbons, C5+feedstock and aromatic hydrocarbons, C6+obtained in the reaction zone of dehydrocyclization. In the zone of separation I liquid-phase process flow is obtained by absorption of hydrocarbons, C3+from the stream exiting the reactor, the first part of the process flow.

Stream III, coming out of the reactor 10 and the resulting contact of the feedstock with the catalyst, cooled in heat exchangers 11.8 and air refrigerator 12 and fed into the absorber 5. From the absorber output absorbent 1, saturated hydrocarbon, C3+the stream exiting the reactor. Coming from the absorber dry gas directed to the transport /flow V/ and recycling /stream VI/. In the stabilization column 3 serves mixture compressed by the compressor 1 raw associated gas XV, condensate XIV and saturated absorbent 1. From the top of the column output stream VIII containing hydrocarbon, C1-C4and non-condensable components of the feedstock, and absorbed in the zone of separation of the stream exiting the reactor.

Pair with the top of the column is cooled in air refrigerator 6, the condensate from the reflux tank 7 ispace 9 and fed into the reactor. The bottom product of the XI stabilizer - stable high-octane gasoline is cooled in heat exchanger 2 and the air cooler 4 and part of it is used as the absorbent, and the carrying amount is withdrawn from the process as a commodity product.

Below are examples of the implementation of the described methods of processing of associated gas and condensates.

Example 1.

The associated gas processing carried out according to the scheme shown in Fig. 1. The target product is a concentrate of aromatic hydrocarbons. In the area reaktsii dehydrocyclization provide contact of the feedstock with a catalyst of the following composition: zeolite DCM /TU 38.401528-85/ - 30% wt., zinc oxide - 2% wt. the aluminum oxide - 60% wt. The catalyst is prepared by extrusion of a mixture of initial components: H-form zeolite DCM /content of sodium oxide is less than 0.1% wt. /, zinc nitrate, aluminum hydroxide; dried and calcined at 550oC 6 hours. The contact of the feedstock with the catalyst is carried out in an adiabatic mode, when 500oC at the inlet of the reactor and a pressure of 2.0 MPa. Physical characteristics of the streams are given in table. 1, the composition of the main threads - in table. 2. The bottom product stabilizer concentrate of aromatic hydrocarbons, sod the n a high-octane component of gasoline.

Example 2.

The associated gas processing carried out according to the scheme shown in Fig. 2, obtaining a concentrate of aromatic hydrocarbons and propane-butane fraction. Use a catalyst of the following composition: zeolite WHC /TU 38.102168-85/ - 30% wt., zinc oxide and 1.8 wt.%, gallium oxide is 0.4 wt.%, aluminum oxide and 67.8% wt. The catalyst is prepared by extrusion of a mixture of zeolite, zinc nitrate and gallium, aluminum hydroxide, dried and calcined at 550oC 6 hours. Conditions of the catalytic process of example 1. Physical characteristics of the streams are shown in table 3, the composition of the main streams in table 4. The resulting concentrate of aromatic hydrocarbons contains /% wt./ benzene - 1.81, the toluene - 10,61, xylenes - 15,78, aromatic hydrocarbon, C9- 12,42 and can be used as a high-octane component of gasoline.

Example 3.

The processing of associated gas and condensate carried out according to the scheme given in Fig. 3, producing high-octane gasoline components including C5+raw condensate and aromatic hydrocarbons, C6+obtained in the reaction zone of the raw condensate containing associated gas components and C4-raw condensate. Catalunya parts, specific chromatographic and condensate composition of raw materials and parts in other threads defined on the basis of its fractional composition and presents pseudocomponents - conditional connections with the calculated boiling points under normal conditions /designation in the table: TC - 5oC, etc./

Example 4.

The processing of associated gas, enriched hydrocarbon, C5+and unstable condensate gasoline hydrocarbons of high octane gasoline carried out according to the scheme given in Fig. 4. With the installation divert stable gasoline and dry gas for transport. The catalyst and conditions dehydrocyclization according to example 1. Table 7 summarizes the physical characteristics of streams in table 8 - composition of the main streams in the same manner as in example 3. Stable gasoline contains at least 62,43% wt. alkyl benzenes, including not less than 7.65% of wt. of benzene.

1. The method of obtaining aromatic hydrocarbons from petroleum gas by the reaction of dehydrocyclization components C3+raw materials for zeolite catalysts, in which the stream leaving the reaction zone and containing hydrogen, alkanes C1- C4and aromatic hydrocarbon, C6+served in zoocasa, containing propane, butane and aromatic hydrocarbons, C6+served I the process flow in the fractionation zone and divide it into at least a second process flow containing propane and butane, and the first product stream containing aromatic hydrocarbons, C6+serving II process flow in the reaction zone of dehydrocyclization, working in conditions of dehydrocyclization, and receive the stream leaving the reaction zone, wherein the vapor stream from the separation zone also contains ethane in the reaction zone is served raw materials containing alkanes C1- C4and part of the vapor stream from the zone of separation.

2. The method according to p. 1, characterized in that the fractionation zone there is also a second product stream containing propane and butane, and remove it from the process.

3. The method according to p. 1, characterized in that the raw material contains a hydrocarbon, C5+and in the reaction zone serves alkanes C1- C4that produce from raw materials in the zone of the fractionation in part II of the flow process and display the first product stream comprising the hydrocarbon, C5+contained in raw materials.

 

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1 tbl, 11 ex

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1 tbl, 1 ex

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