Method of obtaining olefins

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining olefins, including a) steam cracking of an ethane-including raw material in the zone of cracking and under conditions of cracking with obtaining a flow discharged from the zone of cracking, which includes, at least, olefins and hydrogen; b) conversion of the oxygenated raw material in the zone of conversion of oxygenate to olefins in the presence of a catalyst with obtaining a flow, consisting of, at least, olefins and hydrogen, discharged from the oxygenate-to-olefins (OTO) flow; c) combination of, at least, a part of the flow, discharged from the zone of cracking and a part of the flow, discharged from the OTO zone with obtaining a combined output flow; and d) separation of hydrogen from the combined output flow, with the formation of, at least, a part of the oxygenated raw material due to the supply of hydrogen, obtained at stage d), and the raw material, containing carbon oxide and/or carbon dioxide, into the zone of oxygenates synthesis and obtaining oxygenates. The invention also relates to a combined system for the claimed method realisation.

EFFECT: claimed invention makes it possible to obtain target products by the improved combined method of ethane cracking and OTO technology.

8 cl, 1 dwg, 5 tbl, 1 ex

 

The invention relates to a method for producing olefins, unified olefins production.

In recent years increasing attention is paid to the development and use of sources of natural gas around the globe. The disadvantage of natural gas compared to oil is the difficulty of transporting large volumes of natural gas from the field to the place of application. One of effective ways of transporting natural gas is a natural gas liquefaction and transportation of liquefied natural gas (LNG). The other way is the conversion of methane in natural gas into liquid hydrocarbons using the technology transfer of the gas phase in the liquid (GtL). The products of the GtL process are usually liquid and can be transported in the same way as traditional oil and petrochemical products.

In addition to methane, natural gas usually includes other hydrocarbons such as ethane, propane and butanes. Such natural gas is called potenziani gas. The last two can be inserted into a manifold LPG, but ethane cannot be added. In addition, for various reasons, the content of ethane in natural gas supplied to process LNG or GtL, is limited and therefore a significant portion of the ethane must be removed from natural gas before the natural gas is supplied in either LNG or GtL.

X�thee the use of ethane limited, typically the ethane is burned in a furnace to produce heat; its corresponding olefin ethylene is a basic chemical compound that has a wide number of application areas that are of greatest commercial interest. Ethane can be converted to ethylene, for example, when using the process of thermal cracking. Then ethylene can be used to obtain, for example, polyethylene, styrene, ethylene oxide or glycol. The conversion of ethane to ethylene is a highly endothermic reaction and requires a supply of significant amounts of energy. In addition, the capital cost of the process of converting ethane to ethylene, especially at the stage of recycling, and the subsequent processes of conversion of ethylene is high, and requires a minimum production capacity of ethylene to make it economically feasible.

When the ethane content in natural gas is too low, and, accordingly, ethane available is inadequate, the process of converting ethane to ethylene becomes unattractive.

This problem becomes even more pronounced in the case where natural gas is withdrawn from a relatively small gas-bearing strata, especially those located in remote isolated places, also called hard-to-reach natural gas. Of course, this hard-to-reach natural� gas can be converted to LNG or GtL products. However, this requires that in tight gas-bearing reservoir was maintained at the minimum level of productivity daily to ensure the profitability of investments. Usually these hard-to-reach gas-bearing strata cannot ensure the achievement of performance levels sufficient to maintain operation of the process GTL or LNG. In addition, while not getting enough ethane to support the work processes of conversion of ethane to ethylene and subsequent conversion of ethylene.

It was proposed to combine the installation of steam cracking of ethane to oxidation up to olefins (OTO), you can find additional ethylene. For example, C. Eng et al., (C. Eng, E. Arnold, E. Vora, T. Fuglerud, S. Kvisle, H. Nilsen, Integration of the UOP/HYDRO MTO Process into Ethylene Plants, 10thEthylene Producer's Conference, New Orleans, USA, 1998) proposed to merge UOP technology of obtaining olefins from methanol (MTO) with the installation of steam cracking of naphtha or ethane. It is mentioned that by combining the two processes it is possible to obtain a sufficient amount of ethylene with simultaneous production of valuable propylene. The disadvantage referred to E. Eng et al., is fluctuations of prices for methanol, which is the main raw material for the MTO reaction.

In the application WO2009/039948 A2 proposed combined steam cracking process and MTP for producing ethylene and propylene. According to WO2009/039948 A2, this process is achieved �special advantage by combining the final stages of both processes. The original methanol is produced from methane, which requires a sufficient supply of methane.

In US 2005/0038304 disclosed integrated system producing ethylene and propylene from the system of General relativity and steam cracking system. According to US 2005/0038304, in this process, a particular advantage is achieved by combining the final stages of both processes. From synthesis gas produced methanol as the main raw material for the process of General relativity. However, according to US 2005/0038304, the production of methanol from synthesis gas requires a lot of energy due to the endothermic nature of the process of producing synthesis gas, so that the endothermic process of producing synthesis gas is usually steam reforming of methane.

Methanol can be produced from hydrogen and carbon monoxide or carbon dioxide. Usually methanol is prepared from a mixture of hydrogen, carbon monoxide and carbon dioxide. To synthesize methanol, it is necessary to provide hydrogen, carbon oxide and carbon dioxide in a molar ratio of at least 2, and the ratio is calculated as follows:

molar ratio = (# mol H2- # moles of CO2)/(# mol CO + # mol CO2)

The raw material for methanol synthesis is usually the synthesis gas. But, of course, the synthesis gas contains hydrogen, carbon monoxide and carbon dioxide in a molar ratio of at least 2. In most ectothermic�technical processes of synthesis gas, however, there is a synthesis gas, depleted in hydrogen. It is not enough, for example, for transmission of depleted hydrogen synthesis gas through the reactor the conversion of water gas with the conversion of the carbon monoxide in the synthesis gas with water to hydrogen and carbon dioxide. As you can see in the definition of the molar ratio described above, this conversion does not affect the achievable molar ratio. As described in US 2005/0038304, synthetic gas, which is enriched with hydrogen, formed as a result of an endothermic process, such as steam reforming of methane. To reduce the energy consumption in the production of synthesis gas, the synthesis gas is mixed with depleted hydrogen synthesis gas, for example, the resulting exothermic nekataliticheskogo the partial oxidation process. The mixture is then used for methanol synthesis.

In the application WO 2007/142739 A2 the method of producing methanol from synthesis gas. Methanol can be used to produce olefins. In the method proposed in WO 2007/142739A2, the flow of hydrogen containing more than 5 mol.% methane is combined with the synthesis gas. The flow of hydrogen may be obtained, for example, in the steam cracking process.

In US 2002/0143220A1 a method of producing olefins. The hydrocarbon feedstock is subjected to oxidative dehydrogenation to receive Alevi�s and synthesis gas. The synthesis gas is converted into methanol. Methanol can be converted to ethylene.

In this industry there is a need for an improved combined method of cracking of ethane and GRT technology.

It was found that it is possible to obtain olefins by thermal cracking of ethane with the formation of olefins and hydrogen with simultaneous production of additional olefins, using the technology of General relativity, in which the hydrogen obtained from the cracking process and procedure OTO, is used to produce at least part of the oxidized raw material for the process of General relativity.

Accordingly, the present invention relates to a method for producing olefins, comprising

(a) including cracking of ethane feedstock in the cracking zone and the cracking conditions with obtaining leaving the cracking zone of a stream comprising at least olefins and hydrogen;

(b) conversion of the oxidized raw material in the oxidation zone to olefins with getting out of a zone by the flow of at least olefins and hydrogen;

(C) combining at least part of the effluent from the cracking zone flow and parts coming out of the area by the stream with obtaining a combined effluent stream; and

d) separation of hydrogen from the combined effluent stream, forming at least part of the oxidized raw material by supplying hydrogen of step (d) and raw materials containing�the carbon monoxide and/or carbon dioxide, in the area of synthesis of oxygenates and receipt of oxygenates.

A method according to the present invention relates to the production of olefins, particularly lower olefins (C2-C4), more specifically, ethylene and propylene. Several processes, such as cracking of ethane or oxidation processes-to-olefins (OTO), can provide olefins. The process of cracking of ethane and General relativity usually provide obtaining ethylene from various source materials. In the case of phase cracking of ethane feedstock is preferably ethane feedstock. On the other hand, the stage of General relativity involves the use including oxidized compound raw material. Preferred oxidized compounds include allspice and simple alkylamine, more preferably methanol, ethanol, propanol and/or simple dimethyl ether (DME), even more preferably methanol and/or a simple dimethyl ether (DME).

The authors present invention found that upon receipt of olefins United by a process comprising a stage of cracking of ethane and the phase of the conversion of oxygenates to olefins (OTO), a synergistic effect is achieved from the use of raw materials through the use of at least part of the hydrogen obtained in stage (a) cracking of ethane (hereinafter also referred to as the hydrogen that is obtained from stage (a), or hydrogen from the cracking of the unit) and hydrogen, obtained�tion from stage (b) (hereinafter also called hydrogen from process MAPPING), for the synthesis of oxygenates, preferably by conversion of hydrogen in the presence of carbon monoxide and/or carbon dioxide to methanol and/or a simple dimethyl ether.

At the stage (a) of the process which produces hydrogen with olefins, usually hydrogen and olefins out of the cracking zone in the form of effluent from the cracking zone of the stream comprising hydrogen and olefins. Preferably, the hydrogen is separated from the olefins, i.e., the share coming from the cracking zone a stream comprising hydrogen and olefins, before serving in the area of synthesis of oxygenates. Hydrogen can be separated by using suitable means known in this field, for example, cryogenic distillation, absorption, variable pressure, wherein the hydrogen containing hydrogen in the flow is preferable impurities, or through a membrane permeable to hydrogen.

At the stage (b) are formed commodity olefins, which usually leave the area of General relativity in the form emerging from the zone from the stream. This coming from the OTO zone, the flow also includes a small amount of hydrogen, typically in the range from 0.05 to 1 wt.% in the calculation of the total content of hydrocarbons in the effluent from the zone GRT thread. The amount of hydrogen in the effluent from the zone GRT thread, however, is relatively small, which makes the separation of hydrogen from the remainder coming from the area by the stream impractical. In the JV�sobe according to the invention, at least part of the effluent from the cracking zone of the stream and at least part of the effluent from the zone of each stream are combined in the combined effluent at the stage (C), and then at the stage (d) hydrogen is separated from the combined exhaust stream. The hydrogen obtained from the combined effluent stream, called the hydrogen from the combined effluent stream. In this way extract not only part or all of the hydrogen from the effluent from the cracking zone of the stream, but also at least part of the hydrogen from escaping from the area by the stream and used for the synthesis of oxygenates.

These oxygenates are then fed to the OTO reaction to form additional olefins. When using hydrogen from cracking-install and hydrogen from the OTO process reduces if not eliminates altogether, the need for hydrogen-enriched synthesis gas, obtained as a result of the endothermic reforming process. Thus, it reduces the consumption of carbon dioxide for obtaining of oxygenates, as at least part of the hydrogen required for getting the oxygenate, is formed as a by-product and does not add additional carbon dioxide more than what is required for the main reaction product of ethylene.

Directing at least a portion of hydrogen from the cracking of the installation and the hydrogen from the OTO process in the area of synthesis� oxygenates, you can reduce the amount of synthesis gas required for the synthesis of oxygenates, at least compared with only hydrogen from the cracking installation. The synthesis gas is usually obtained by partial oxidation of hydrocarbons using mainly pure oxygen or at least oxygen-enriched air. Production of pure oxygen requires high power consumption, therefore, reduction in the synthesis gas also reduces the need for oxygen, which, in turn, leads to lower consumption of energy and production of carbon dioxide. In addition, can be reduced capex, as it requires less volume of a unit for production of oxygen.

Figure 1 is a diagram of a variant of implementation of the joint system for obtaining olefins according to the invention.

At the stage (a) of the process containing the ethane feedstock is sent to the cracking zone and krakeroy. The resulting product cracking includes olefins and hydrogen.

At the stage (b) of the method oxygendemand raw materials are sent into the zone of conversion of the oxygenate to olefins and convert to obtain at least olefins and hydrogen. Achieved synergy in the method of the invention when using the hydrogen obtained in stage (a) and (b) obtaining at least part oxygenating raw materials in the area of General relativity. As a result, hydrogen, sex�Chennai during the stage of cracking, no longer is burned as fuel in a butane burner, and is used for obtaining valuable oxygenates. In addition, the hydrogen produced in stage (a), does not include significant amounts of inert gases such as N2, Ar or CH4. These inert gases can usually be contained in natural gas or purified oxygen supplied for producing synthesis gas for methanol production. Through the use of hydrogen obtained in stage (a) as part of raw materials for the synthesis of oxygenates, the content of inert gases in this raw material can be reduced.

Achieved additional synergies, since the method of the invention allows the use of mixed raw material, for example, mainly methane/ethane feedstock to produce ethylene. In this case the raw material is separated into a stream comprising primarily ethane, which krakeroy to ethylene, and a stream comprising predominantly methane, which is converted to syngas, and then methanol and/or DME. Methanol and/or DME can be converted to ethylene technology GRT. As a result, the production of ethylene is less prone to the fluctuations of supply as raw material either methane or ethane.

As mentioned above, the hydrogen produced in stage (d), are used to obtain at least part oxygenating raw material supplied to the process area GRT n� stage (b). May be prepared by any suitable oxygenate or mixture of oxygenates, in particular, allspice and simple alkyl esters, preferably methanol and/or DME.

In the method of the invention hydrogen and the raw material containing carbon monoxide and/or carbon dioxide, is fed into a zone for the synthesis of oxygenates.

Methanol can be produced directly from hydrogen and at least one of carbon monoxide and carbon dioxide in the zone of synthesis of oxygenates. Hydrogen can interact with carbon monoxide to produce methanol according to the following reaction:

CO+2H2→SN3HE

Alternatively, hydrogen can interact with carbon dioxide the formation of methanol by the following reaction:

CO2+3H2→SN3HE+H2About

It is also possible to use a mixture of carbon monoxide and carbon dioxide. Preferably, the hydrogen and carbon monoxide and/or carbon dioxide is fed to a zone of the synthesis of oxygenates in a molar ratio lying in the range from 2.0 to 3.0, preferably from 2.0 to 2.2. The mole ratio here is defined as follows:

molar ratio = (# mol H2- # moles of CO2)/(# mol CO + # mol CO2)

In the aforementioned definition, at least one the number of moles of carbon monoxide or the number of moles of carbon dioxide is greater than zero.

In the case of cm�si carbon monoxide and carbon dioxide for the conversion of hydrogen into methanol, preferably, the concentration of carbon dioxide in hydrogen, mixtures of carbon monoxide and carbon dioxide was in the range of from 0.1 to 25 mol.%, preferably from 3 to 15 mol.%, more preferably from 4 to 10 mol.%, in the calculation of the total number of moles of hydrogen, carbon monoxide and carbon dioxide in the mixture. The content of carbon dioxide on the content of CO in the syngas must be high enough to maintain an appropriately high reaction temperature and to minimize the amount of undesirable by-products such as paraffins. At the same time, the relative content of carbon dioxide to carbon monoxide should not be too high, or the reaction of carbon dioxide with hydrogen gave less methanol in the hydrogen supplied to the zone of the oxygenate synthesis. Furthermore, the reaction of carbon dioxide with hydrogen is accompanied by the formation of water. If it is found in high concentrations, the water may deactivate the catalyst synthesis of oxygenates.

In the area of the oxygenate synthesis of hydrogen and carbon monoxide and/or carbon dioxide are converted into methanol in the presence of a suitable catalyst. These catalysts are known in this field and are described, for example, in WO 2006/020083 that was put into this document by reference. A suitable catalyst for the synthesis of methanol from nitric acid�and, at least one of carbon monoxide and carbon dioxide includes

Oxide of at least one element selected from the group consisting of copper, silver, zinc, boron, magnesium, aluminum, vanadium, chromium, manganese, gallium, palladium, osmium and zirconium. Preferably the catalyst is a catalyst based on copper and zinc, more preferably in the form of copper, copper oxide and zinc oxide.

A catalyst based on copper, which includes an oxide of at least one element selected from the group consisting of silver, zinc, boron, magnesium, aluminum, vanadium, chromium, manganese, gallium, palladium, osmium and zirconium. Preferably the catalyst contains copper oxide and an oxide of at least one element selected from the group consisting of zinc, magnesium, aluminum, chromium and zirconium.

A catalyst selected from the group consisting of oxides of copper, oxides of zinc and aluminum oxides. More preferably, the catalyst contains oxides of copper and zinc.

- A catalyst comprising copper oxide, zinc oxide and at least one other oxide.

Preferably, at least one other oxide selected from the group consisting of zirconium oxide, chromium oxide, vanadium oxide, magnesium oxide, aluminum oxide, titanium oxide, hafnium oxide, molybdenum oxide, tungsten oxide, and manganese oxide.

Especially coming�their catalysts include catalysts, containing copper oxide in the range from 10 to 70 wt.% in the calculation of the total mass of the catalyst. Preferably containing copper oxide in the range of 15 to 68 wt.% and more preferably from 20 to 65 wt.% copper oxide, based on the total weight of the catalyst.

This catalyst may preferably also contain zinc oxide in the range from 3 to 30 wt.% in the calculation of the total mass of the catalyst. Preferably comprise zinc oxide in the range from 4 to 27 wt.%, more preferably from 5 to 24 wt.% zinc oxide in the calculation of the total mass of the catalyst.

A catalyst comprising both copper oxide and zinc which preferably comprises copper oxide and zinc oxide in the ratio of copper oxide to zinc oxide, which can vary over a wide range. Preferably the catalyst comprises copper oxide to zinc oxide in an atomic ratio of Cu:Zn in the range from 0.5:1 to 20:1, preferably from 0.7:1 to 15:1, more preferably from 0.8:1 to 5:1.

The catalyst can be obtained according to known methods. Examples of these methods can be found in U.S. patents№№ 6114279; 6054497; 5767039; 5045520; 5254520; 5610202; 4666945; 4455394; 4565803; 5385949, where the description of each is fully introduced in this document by reference.

Methanol can be synthesized in the zone of the oxygenate synthesis according to any conventional techniques for the synthesis of methanol. Examples of these processes include periodic �rezessy and continuous processes. Continuous processes are preferred.

Processes in a tubular layer and processes in the fluidized bed are particularly preferred types of continuous processes.

The methanol synthesis process is effective in a wide range of temperatures. Preferably, the methanol is synthesized in the zone of the oxygenate synthesis of the implementation of the contact of hydrogen and at least one of carbon monoxide and carbon dioxide with the catalyst at a temperature in the range from 150 to 450°C, more preferably from 175 to 350°C, even more preferably from 200 to 300°C.

The methanol synthesis process is effective in a wide range of pressures. Preferably, the methanol is synthesized by implementation of contact of hydrogen and at least one of carbon monoxide and carbon dioxide with the catalyst in the zone of the oxygenate synthesis at a pressure in the range of 15 to 125 atmospheres, more preferably from 20 to 100 atmospheres, even more preferably from 25 to 75 atmospheres.

For the synthesis of methanol hourly space velocity of gas in the area of synthesis of oxygenate vary depending on the type of a continuous process, which is used. Preferably hourly volumetric velocity of the gas in the gas flow through the catalytic layer is in the range from 50 h-1up to 50000 h-1. Preferably hourly volumetric velocity of the gas in the gas flow certcertificate layer is in the range from about 250 h -1up to 25,000 h-1, more preferably from about 500 h-1up to 10,000 h-1.

The methanol synthesis process, as discussed above herein, may allow to obtain several oxygenates as by-products, including aldehydes and other alcohols. These by-products are also suitable reactants for the reaction GRT. Other less desirable by-products can be removed from effluent from the zone of synthesis of oxygenates stream, if necessary, before serving emerging from the synthesis of oxygenates flow in the OTO area with obtaining at least part oxygenating raw materials.

Other suitable and preferred oxygenate, which can be synthesized in the area of synthesis of oxygento, is a simple dimethyl ether (DME). DME can be directly synthesized from hydrogen, obtained in stage (d), and at least one of carbon monoxide and carbon dioxide, but preferably it is synthesized from methanol, which was at least partly derived from a hydrogen of step (d), as discussed above in the text of this document. Optional DME is produced from methanol and hydrogen and at least one of carbon monoxide and carbon dioxide. Conversion of methanol to DME is known in this field. This conversion is equilibrium �eakley. By conversion of the alcohol is in contact at elevated temperature with a catalyst. In EP-A-340576 presents a list of possible catalysts. These catalysts include the chlorides of iron, copper, tin, manganese and aluminium, and the sulphate of copper, chromium and aluminum. In addition, there may be used oxides of titanium, aluminum and barium. Preferred catalysts include aluminum oxides and aluminum silicates. Alumina is a particularly preferred catalyst, especially gamma-alumina. Although methanol may be in the liquid phase, the process is preferably carried out so that the methanol is in the vapor phase. In this context, the reaction is suitably carried out at a temperature from 140 to 500°C, preferably from 200 to 400°C and a pressure of from 1 to 50 bar, preferably 8 to 12 bar, the exact choice depends on the acidity of the catalyst. Given the exothermic conversion of methanol to DME, the conversion is suitably carried out with cooling of the reaction mixture comprising the first catalyst, the yield of DMF was maximum.

Appropriately, the reaction of methanol conversion to DME runs in a separate section of the zone of synthesis of oxygenates.

In the case when a part of the synthesized methanol is converted into DME extending from the zone of the oxygenate stream may include methanol and DME in any respect. Prefer�till then the mass ratio of DME to methanol is in the range from 0.5:1 to 100:1, more preferably from 2:1 to 20:1. Appropriately, the reaction conversion of methanol to DME is a reaction leading to the equilibrium. This implies that the mass ratio of DME to methanol can vary from 2:1 to 6:1. Obviously, the person skilled in the art may decide the question of the displacement of the equilibrium by creating different reaction conditions and/or the introduction or withdrawal of any of the reactants.

In the method according to the invention, at least part oxygenating feedstock is methanol and/or DME, obtained by the reaction of hydrogen obtained in stage (d) at least one of carbon monoxide and carbon dioxide.

The raw material containing carbon monoxide and/or carbon dioxide, may be any available raw materials containing carbon monoxide and/or carbon dioxide. A particularly suitable raw material containing carbon monoxide and/or carbon dioxide, is the source that includes the synthesis gas obtained in the process for producing synthesis gas. The process for producing synthesis gas preferably includes acatalasemia the process of partial oxidation, catalytic partial oxidation processes, the processes of steam reforming of methane, the processes Autoterminal reforming and water gas shift. Although the process of conversion of water gas is a process for producing synthesis gas coming �of the process of conversion of water gas stream typically includes hydrogen, carbon monoxide, carbon dioxide. The source also may include synthesis gas derived from several processes for producing synthesis gas.

The preferred sources of carbon monoxide and/or carbon dioxide are those that include the synthesis gas having a mole ratio of hydrogen and carbon monoxide and/or carbon dioxide, as defined above in the text of this document, below which the relationship is preferred for methanol synthesis, i.e. the sources are deficient in hydrogen. Data synthesis gases obtained from processes for producing synthesis gas, in which natural gas or other methanogenesis gas is subjected to partial oxidation to obtain a raw synthesis gas for the Fischer-Tropsch process. These processes for producing synthesis gas preferably include non-catalytic partial oxidation processes, catalytic partial oxidation processes and processes Autoterminal reformer.

Preferably, the synthesis gas used as feedstock containing carbon monoxide and/or carbon dioxide has a molar ratio of hydrogen to carbon monoxide and/or carbon dioxide in the range from 1.0 to 1.9, more preferably from 1.3 to 1.8, where the molar ratio is determined as defined above. This synthesis gas with a low content of carbon dioxide is preferred�flax get non-catalytic methods of partial oxidation to produce synthesis gas. The partial oxidation catalyst is normally induces the conversion of water gas in the presence of water. As a result, the carbon monoxide is converted into carbon dioxide. An additional advantage is that the non-catalytic partial oxidation processes do not require the addition of significant quantities of water for the process of catalytic partial oxidation process. Processes produce significant amounts of carbon dioxide include, for example, steam reforming of methane. Therefore, the use of synthesis gas process steam reforming of methane is less desirable.

The method of the invention includes variants of implementation, in which the hydrogen of step (d) use and/or mixed with withdrawing from the process of obtaining singata flow and then at least part of the stream, optionally after processing at the stage of conversion of water gas, used for the synthesis of oxygenates.

The use of a portion of the synthesis gas, the remainder of which is used as raw material for Fischer-Tropsch process, has the additional advantage, which is that carbon dioxide in the stream of synthesis gas can be advantageously directed to the synthesis of oxygenates, and not in the Fischer-Tropsch process, in which carbon dioxide is considered to�to unwanted inert impurity.

Other suitable raw materials containing carbon monoxide and/or carbon dioxide, is a source comprising carbon dioxide obtained from natural gas fields or oil formation. This carbon dioxide is also referred to as oil field carbon dioxide. Some deposits of natural gas or oil-bearing strata include significant concentrations of carbon dioxide, up to 70 mol.% in the calculation of the total volume of gas extracted from the reservoir. When you use this carbon dioxide for the synthesis of oxygenates olefins and then the carbon dioxide is captured, reducing the penalty for carbon dioxide in the development of natural gas fields or oil reservoirs.

Other suitable raw materials containing carbon monoxide and/or carbon dioxide, is a source comprising carbon dioxide obtained from containing carbon dioxide stream of flue gas, in particular flue gas obtained from the pooled process according to the invention, or optionally from purification of oxygen or from the process of producing synthesis gas. Preferably the flue gas is first concentrated to increase the concentration of carbon dioxide.

A particularly suitable raw material containing carbon monoxide and/or carbon dioxide, can be the source that includes the flue gas obtained by oxidative�the individual oxodolini of a furnace for cracking ethane, usually one of the furnaces for cracking of ethane used in obtaining olefins in step (a). In the case of oxidative cocodamine from the furnace using pure oxygen or pure oxygen diluted with carbon dioxide instead of air, can be obtained by a stream of essentially pure carbon dioxide, which is particularly suitable for inclusion in materials containing carbon monoxide and/or carbon dioxide. Although at first it is necessary to obtain pure oxygen, it is not necessary to additionally process the flue gas to capture carbon dioxide. In addition, koksouglej with the OTO catalyst during catalyst regeneration can be carried out similarly with obtaining appropriate including carbon dioxide stream.

Other particularly suitable raw material containing carbon monoxide and/or carbon dioxide, may be a source comprising carbon dioxide obtained by oxidative cocodimonium with a catalyst, such as catalyst for conversion of oxygenates used in the process of General relativity.

Other particularly suitable raw material containing carbon monoxide and/or carbon dioxide, may be a source comprising carbon dioxide obtained from the process of obtaining ethylene oxide or monoethylene glycol (MEG).

As noted above, it is preferable to use raw materials, soda�containing carbon monoxide and/or carbon dioxide, which includes carbon monoxide, and carbon dioxide, therefore, preferably the synthesis gas is combined with at least one stream comprising carbon dioxide, with the receipt of raw materials containing carbon monoxide and/or carbon dioxide. For example, a synthesis gas comprising mainly hydrogen and carbon monoxide, can be combined with gas production carbon dioxide with obtaining raw materials containing carbon monoxide and/or carbon dioxide, which can be mixed, at least part of the hydrogen obtained in stage (d). Preferably the synthesis gas to add enough carbon dioxide to obtain the concentration of carbon dioxide in the range from 0.1 to 25 mol.%, preferably from 3 to 15 mol.%, more preferably from 4 to 10 mol.%, in the calculation of the total number of moles of hydrogen, carbon monoxide and carbon dioxide in the mixture.

Preferably use the synthesis gas that includes or does not include carbon dioxide. Carbon dioxide, for example, of the MEG process, includes or does not include inert compounds, such as Ar, N2or CH4. When using synthesis gas with a low content or absence of carbon dioxide content, you can add more carbon dioxide, for example, of the MEG process, and less inert compounds will fall into the zone of synthesis of oxygenates. Thus, �brushetta less exhaust of carbon dioxide, what, otherwise, would require its separation or removal and storage.

Combining at least a portion of the effluent from the cracking zone of the stream and at least part of the effluent from the zone by the flow in the combined output stream will also be combined into a single stream, at least part of the olefins obtained in stage (a) and phase (b).

Considering the raw materials, which includes mainly ethane, leaving the cracking zone, the flow obtained in the cracking zone in step (a), will include mainly ethylene, but may also include up to 2 wt.% propylene based on the total weight of the ethylene in the effluent from the cracking zone thread. This amount of propylene is not economically renewable, however, the Association of olefins, obtained from the cracking zone in step (a), and olefins obtained from the OTO zone at the stage (b), i.e. by Association, at least part of the effluent from the cracking zone of the stream and at least part of the facing and areas by stream combined into a single output stream, get a combined effluent stream that comprises in the range from 10 to 40 wt.% propylene, based on the total content of hydrocarbons in the effluent of the United. The high content of propylene in the effluent of the United due to the high content of propylene in the effluent from the zone GRT thread. In the process FROM� yields a mixture of olefins, including the range from 5 to 80 wt.% of ethylene and in the range from 10 to 80 wt.% propylene, based on the total content of hydrocarbons in the effluent from the zone GRT thread. Combining the streams issuing from the cracking zone and from the zone OTOH, it is also possible to economically extract propylene from leaving the cracking zone of the stream. Propylene can be used as raw material for the process of obtaining polypropylene, optionally after processing it to remove impurities. Processes for the production of polypropylene is well known in this field.

In addition to olefins and hydrogen, the OTO process is also accompanied by the formation of small amounts of alkanes, in particular ethane, propane and butane. Additional benefits from the joint process can be obtained by applying any of the ethane present in effluent from the zone GRT stream in the cracking zone. Ethane can then be krejcirova to ethylene and hydrogen in the cracking zone, thus providing an additional amount of ethylene and hydrogen. The hydrogen can then be used for the synthesis of oxygenates.

One of the olefins obtained at both stages (a) and (b) of the method according to the invention is preferably ethylene. Preferably, the ethylene obtained in stage (a), together with ethylene, obtained in stage (b), preferably in a combined output stream.

Ethylene, sex�built in the method according to the invention, can be used as raw material for several other processes, including the production of ethylene oxide, monoethylene glycol (MEG) and Monomeric styrene.

The inventors, it was found that it is possible to combine the production of these products in the method of the invention with additional positive effect.

When you first supplementary merging at least a portion of the ethylene obtained in stage (a) stage (b), or preferably at both stages (a) and (b), is oxidized to ethylene oxide by supplying at least part of the ethylene with oxygen in the oxidation zone of ethylene, hereinafter referred to as the area of the EO.

Preferably, the ethylene oxide is additionally converted to monoethylene glycol (MEG). MEG is a liquid and therefore can be transported and stored more conveniently than ethylene oxide. Preferably the area EA is part of a larger area of the synthesis of monoethylene glycol, i.e., the second zone of the oxygenate synthesis, hereinafter called area MEG. Preferably, the zone of MEG comprises a first section that includes the area EA, and the second section of the hydrolysis of ethylene oxide. MEG synthesize, providing the ethylene oxide source of water in the zone of hydrolysis of ethylene oxide and converting the ethylene oxide to MEG. Optional first interact ethylene oxide with carbon dioxide � the formation of ethylene carbonate, which is then hydrolysed with getting MEG and carbon dioxide, in accordance with reference in this document to US 2008139853 introduced in this document by reference.

Ethylene is usually converted into ethylene oxide by oxidation of ethylene to form ethylene oxide.

The conversion of ethylene to ethylene oxide can be carried out by any method of oxidation of ethylene, which is formed of at least ethylene oxide and carbon dioxide. In the area of EE, at least part of the ethylene is partially oxidized with the formation of ethylene oxide. Preferably, the ethylene oxidation occurs in the area of EE, which serves the ethylene and the oxygen source. Preferably the oxygen source is oxygen-enriched air, more preferably pure oxygen. Oxidation of oxygen can be carried out over the catalyst in the first section, preferably a catalyst based on silver. Reference to, for example, to work Knile et al., Ethylene, Keystone to the petrochemical industry, Marcel Dekker Inc., New York, 1980, especially page 20. As a by-product during the oxidation of ethylene to ethylene oxide carbon dioxide produced. Not wishing to be bound by theory, the inventors believe that the production of carbon dioxide based on the interaction of ethylene with associated with catalyst oxygen atoms. As a consequence et�, from 14 to 20 mol.% of the total amount of ethylene introduced into the zone EO, turns into carbon dioxide.

Conversion of ethylene oxide to MEG can be accomplished using the process of obtaining a MEG, which uses ethylene oxide. Typically, the ethylene oxide is hydrolysed with water to MEG. Optional ethylene oxide is first converted with the aid of carbon dioxide in the ethylene carbonate, which is then hydrolysed to MEG and carbon dioxide. Water is fed into the zone of MEG as a source of water, preferably pure water or steam. Trademarks get MEG MEG from the zone in the form including MEG outgoing flow. Appropriate ways to obtain ethylene oxide and MEG suggested, for example, in patent applications US 2008139853, US 2009234144, US 2004225138, US 20044224841 and US 2008182999 introduced in this document as references, but may be used any suitable method for obtaining ethylene oxide and the conversion of ethylene oxide to MEG.

As indicated, a by-product of the process of ethylene oxide/MEG is carbon dioxide. During the oxidation of ethylene to ethylene oxide carbon dioxide produced. This waste carbon dioxide, and it needs to be insulated or otherwise allocate and store. In the method according to the present invention, this carbon dioxide can be used to obtain at least part of raw materials containing carbon monoxide and/or carbon dioxide�Yes, introduced into the zone of synthesis of oxygenate.

Preferably carbon dioxide is removed from leaving the area EA flood with obtaining individual comprising carbon dioxide stream. Preferably dispensed from the EO zone, the flow is further treated by conversion of ethylene oxide to MEG in the area of MEG. From the zone get MEG out of a zone of MEG stream, including MEG and carbon dioxide. Appropriate carbon dioxide can be separated from exiting the zone MEG stream by cooling of the exhaust zones MEG stream to a temperature below the boiling point MEG, this carbon dioxide is also referred to as carbon dioxide from MEG. Since the additional carbon dioxide is not formed in the conversion of ethylene oxide to MEG, carbon dioxide from MEG is the same as carbon dioxide from EA. With repeated use of carbon dioxide for the synthesis of oxygenates reduces the consumption of fresh carbon dioxide to obtain EA. Another advantage is that the stream comprising carbon dioxide obtained from the area of EO or MEG, which comprises mainly carbon dioxide and, depending on the flow temperature, vapor. Preferably, the stream includes carbon dioxide and steam in the range of from 80 to 100 mol.%, in the calculation of the total number of moles in the stream. More preferably, the stream comprising carbon dioxide, includes mainly� only carbon dioxide and optionally steam. Such a stream is particularly suitable for use in the synthesis of oxygenates, as it does not introduce significant amounts of inert substances, such as CH4N2and Ar, in the area of synthesis of oxygenates. However, if the stream comprising carbon dioxide, includes significant amounts of other undesirable compounds, e.g., ethylene oxide, the stream is preferably treated to remove these compounds prior to introduction of the stream into the zone of synthesis of oxygenates. Usually during the oxidation of ethylene oxide in the EO contains small amounts of chlorinated compounds. As a result, the stream comprising carbon dioxide obtained from the area of EO and MEG, may include alkylchloride. The content of alkylchloride in the stream comprising carbon dioxide obtained in the area of EO and MEG may be determined using known methods of analysis for determining the composition of the gas flow, such as gas chromatography. In the case when the stream comprising carbon dioxide obtained in the area of EO or MEG, includes alkylchloride, the stream comprising carbon dioxide obtained in the area of EO or MEG, preferably first treated with removal of alkylchloride. Chlorine can be removed using any suitable method for removing the chlorine from the gas stream. One such method involves the desorption process or �xtraction of alkylchloride in the extraction plant. Another suitable process includes removal of alkylchloride membranes.

Another advantage of the Association with the synthesis of MEG is that after MEG during the process of obtaining MEG in the area of the MEG can form small amounts of other oxygenates, such as, for example, diethylene glycol. These oxygenates can be appropriately separated from the effluent from the zone of MEG stream and sent to the OTO area as part oxygenating raw materials.

The second additional Association can be achieved at a conversion of at least part of the ethylene obtained in stage (a) stage (b), or preferably both stages (a) and (b) in the presence of benzene to ethylbenzene conversion of at least part of the ethylbenzene in Monomeric styrene and at least hydrogen.

Each of the mentioned stages of conversion are well known in this field. Can be used by any suitable process. Ethylbenzene usually get in the interaction of ethylene and benzene in the presence of acid catalyst. Reference to, for example, to work Knile et al., Ethylene, Keystone to the petrochemical industry, Marcel Dekker Inc., New York, 1980, especially the part 3.4.1, page 24-25. Although styrene receive catalytic dehydrogenation of ethylbenzene in the presence of a suitable catalyst, examples of suitable catalyst VK�ucaut, but are not limited to, dehydrogenation catalysts based on iron oxide (III).

Combining the method of the invention with obtaining Monomeric styrene, as discussed above, receive an additional hydrogen after desirable products. Preferably the hydrogen is separated from the other reaction products and then sent to the area of the synthesis of oxygenates to receive at least part oxygenating raw material for stage (b) of the process.

When using hydrogen obtained by reforming of ethylene using ethylbenzene in styrene for the synthesis of oxygenates reduces the consumption of fresh carbon dioxide for obtaining of oxygenates, as at least part of the required to obtain oxygenate the hydrogen is produced as a by-product, and optionally carbon dioxide do not add more than what is required to produce styrene as the main reaction product.

The obtained Monomeric styrene can be used to produce polystyrene.

In one of the embodiments, the invention includes

(i) providing a feedstock comprising methane and ethane;

ii) separation of the raw material at least on raw, containing methane, and raw materials containing ethane;

iii) providing at least part of the methane feedstock for the process of producing synthesis gas to produce synthesis gas;

and (iv) innings�, at least part of the ethane in the cracking zone and at least part of the synthesis gas in the area of synthesis of oxygenates.

In this way, the invention allows for the joint receipt of ethylene and propylene from a feedstock comprising methane and ethane, such as, for example, natural gas or associated gas. The mention herein of associated gas refers to C1-C5 hydrocarbons, obtained jointly in the extraction of oil.

In the present invention include ethane feedstock is subjected to cracking in a cracking zone at cracking conditions to obtain at least olefins and hydrogen.

In addition, the formation of a small amount of propylene. May form other by-products, such as butylene, butadiene, Atin, propin and benzene. The cracking process is carried out at elevated temperatures, preferably in the range from 650 to 1000°C, more preferably from 750 to 950°C. Typically, the cracking is carried out in the presence of water (steam) as diluent. The conversion of ethane is typically a value in the range from 40 to 75 mol.% in the calculation of the total number of moles of ethane introduced in hon cracking. Preferably nakikiramay Ethan sent for recycle back to the cracking zone. The process of cracking of ethane is well known to specialists in this field and do not require additional explanation. Reference to, for example, to work Knile et al., Ethyene, Keystone to the petrochemical industry, Marcel Dekker Inc., New York, 1980, especially Chapter 6 and 7.

In the present invention oxygendemand raw material is converted in the process of an oxygenate-to-olefins, in which the contact oxygenating raw materials in the area of General relativity with the catalytic conversion of oxygenate in the conditions of conversion of the oxygenate with the receipt coming out of the conversion process stream comprising lower olefins. In the area of General relativity, at least a portion of the feedstock is converted into a product containing one or more olefins, preferably including light olefins, especially ethylene and/or propylene.

Examples of oxygento that can be used in oxygendemand raw materials at the stage b) of the process include alcohols such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol; ketones, such as acetone and methyl ethyl ketone; aldehydes, such as formaldehyde, acetaldehyde and Propionaldehyde; ethers, such as simple dimethyl ether, simple diethyl ether, simple metaliteracy ether, tetrahydrofuran and dioxane; epoxides such as ethylene oxide and propylene oxide; and acids such as acetic acid, propionic acid, formic acid and butyric acid. Additional examples are diallylmalonate, such as dimethylcarbonate, or complex alkyl esters of carboxylic acids such as methyl formate. From the data of example�in a preferred are alcohols and ethers.

Examples of preferred oxygenates include alcohols, such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol; and simple dialkyl ethers, such as simple dimethyl ether, simple diethyl ether, metaliteracy ether. Simple cyclic ethers such as tetrahydrofuran and dioxane, are also appropriate.

The oxygenate used in the method according to the invention is preferably an oxygenate, which includes at least one related oxygen-alkyl group. Alkyl group is preferably C1-C4 alkyl group including from 1 to 4 carbon atoms; more preferably an alkyl group comprises 1 or 2 carbon atoms and most preferably one carbon atom. The oxygenate may include one or more data connected by oxygen, C1-C4 alkyl groups. Preferably, the oxygenate comprises one or two oxygen, C1-C4 alkyl group.

More preferably, use of the oxygenate having at least one C1 or C2 alkyl group, also more preferably, at least one C1 alkyl group.

Preferably, the oxygenate is selected from the group alkanols and simple dialkylated esters comprising dimethyl ether, simple diethyl ether, simple mutilative ether, methanol, this�Ola and isopropanol and mixtures thereof..

Most preferably originator is methanol or a simple dimethyl ether or a mixture thereof.

Preferably oxygendemand feedstock comprises at least 50 wt.% oxygenate, in particular methanol and/or dimethyl ether, based on total hydrocarbons, more preferably at least 80 wt.%, most preferably at least 90 wt.%.

Oxygendemand raw materials can be obtained from the preliminary reactor in which methanol is converted at least partially into a simple dimethyl ether. Thus, it is possible to remove water by distillation, resulting in less water will be present in the process of converting oxygenate to olefins, which is of advantage for the process and reduces the hardness of hydrothermal conditions affecting the catalyst.

Oxygendemand raw material may include any quantity of diluents, such as water or steam.

There are several OTO processes for the conversion of oxygenates, such as, for example, methanol or simple dimethyl ether to a product containing olefins, as has been discussed above. One such process is described in WO-A 2006/020083 introduced in this document in reference, particularly in paragraphs [0116] to[0135]. Processes that integrate production of oxygenates from synthesis gas and their con�the version in light olefins, reviewed in US 2007/0203380A1 and US 2007/0155999A1.

Catalysts as described in WO And 2006/020083, suitable for conversion oxygenating raw materials at the stage (b) of the present invention. These catalysts preferably include a catalytic composition based on molecular sieves. Suitable molecular sieves are craniologist (SAPO), such as SAPO-17, -18, -34, -35, -44, but also SAPO-5, -8, -11, -20, -31, -36, -37, -40, -41, -42, -47 and -56.

In the alternative, conversion of oxygenating raw materials can be performed using a catalyst based on aluminosilicate, especially zeolite. Suitable catalysts include those containing a zeolite of the group of ZSM, in particular of the MFI type, such as ZSM-22, type MTT, such as ZSM-23, the TON type, such as ZSM-22, the MEL type, such as ZSM-11, the FER type. Other suitable zeolites are, for example, zeolites STF-type, such as SSZ-35, type SFF, such as SSZ-44 and EU-2 type, such as ZSM-48. Catalysts based on aluminum silicates are preferred when concomitant olefin feedstock is supplied to the conversion zone oxygenate together with oxygenate to increase production of ethylene and propylene.

The reaction conditions for the conversion of oxygenates include those mentioned in WO-A 2006/020083. Therefore, the suitable reaction conditions are a reaction temperature of 200 to 1000°C, preferably from 250 to 750°C and a pressure from 0.1 kPa (1 �bar) to 5 MPa (50 bar), preferably from 100 kPa (1 bar) to 1.5 MPa (15 bar).

Particularly preferred process of the GRT for use in stage (b) of the present invention will be discussed below. This process provides a particularly high conversion oxygenating raw materials and collateral circulation of raw materials to ethylene and propylene. In this regard, reference is made to WO 2007/135052, WO 2009/065848, WO 2009/065875, WO 2009/065870, WO 2009/065855, WO 2009/065877, which uses a catalyst comprising an aluminosilicate or zeolite having one-dimensional 10-core channels, concomitant olefin feedstock and/or circulation of material.

In this process the catalyst for conversion of oxygenates comprises one or more zeolites having one-dimensional 10 - core channels that are not intersected by other channels, preferably at least 50 wt.% these zeolites in the calculation of the total amount of zeolite in the catalyst. Preferred examples are zeolites of the MTT and/or TON type. In a particularly preferred embodiment the catalyst comprises in addition one or more one-dimensional zeolites having 10-core channels, such as MTT and/or TON type, a more multi-dimensional zeolite, in particular of the MFI type, more specifically ZSM-5, or of the MEL type, such as zeolite ZSM-11. This additional zeolite (molecular sieve) can have a positive effect on the stability of the catalyst in the course� process in General relativity and hydrothermal conditions. A second molecular sieve having more multidimensional channels, has intersecting channels in at least two directions. For example, the structure of channels formed essentially parallel channels in the first direction and substantially parallel channels in a second direction, where the channels in the first and second directions intersect. It is also possible crossing with the channels of the other type. Preferably, the channels in at least one direction are a 10-core channels. The preferred zeolite of MFI type has a ratio of silicon dioxide to aluminum oxide, SAR of at least 60, preferably at least 80, more preferably at least 100, even more preferably at least 150. The catalyst for conversion of oxygenates may include at least 1 wt.% in the calculation of the total weight of molecular sieve in the catalyst of the conversion of oxygenates second molecular sieve having one-dimensional channels, preferably at least 5 wt.%, more preferably at least 8 wt.%, and in addition may include less than 35 wt.% additional molecular sieves, in some embodiments, less than 20 wt.% or less than 18 wt.%, for example, less than 15 wt.%.

Especially when the conversion of oxygenate is carried out over a catalyst containing the aluminosilicate MT� TON and types, may be preferential to enter the associated raw material containing an olefin, together with oxygendemanding raw materials (such as enriched simple dimethylethylene ether and washed with methanol raw material) in the area of General relativity, when the last of the raw material is introduced into this zone. It was found that the catalytic conversion of oxygenates, particularly methanol and DME, ethylene and propylene is accelerated when the olefin is in contact between the methanol and/or simple dimethylethylene ether and catalyst. Therefore, appropriate concomitant olefin feedstock in the reaction zone together with oxygendemanding raw material.

In particular embodiments, at least 70 wt.% olefin related raw materials produced in the course of normal operation due to the circulating flow C3+ or C4+ olefin fraction from coming out of the conversion process by the stream, preferably at least 90 wt.%, more preferably at least 99 wt.% and most preferably concomitant olefin raw materials during normal operation, is formed by this circulating flow. In one of the embodiments of the invention concomitant olefin feedstock can include at least 50 wt.% C4 olefins and at least 70 wt.% C4 hydrocarbon compounds. It can also include propylene. Outgoing� from the OTO conversion process flow may include 10 wt.% or less preferably 5 wt.% or less, more preferably 1 wt.% or less C6-C8 aromatics, based on total weight of hydrocarbons in the effluent. At least one concomitant olefin feedstock and the circulation flow can, in particular, contain less than 20 wt.% C5+ olefins, preferably less than 10 wt.% C5+ olefins, based on the total weight of hydrocarbons in olefin-related raw materials.

To maximize the formation of ethylene and propylene, it is desirable to maximize the circulation of C4 olefins. In the offline process, i.e. without combining with the cracking installation, there is a limit for the maximum circulation of the C4 fraction of the flow coming from the GRT zone. Some part of it that lies between 1 and 5 wt.%, must be withdrawn as purge, since otherwise saturated C4 hydrocarbons (butane) will form deposits that are substantially not converted under the reaction conditions of General relativity.

In a preferred method the optimum yield of light olefins when OTO conversion is carried out at a temperature over 450°C, preferably at a temperature of 460°C or higher, more preferably at a temperature of 480°C or higher, especially at 500°C or higher, more particularly at 550°C or higher, or 570°C or higher. The temperature typically is less than about 700°C or less than 650°C. Galleriesnude typically lie between 0.5 and 15 bar, in particular, between 1 and 5 bar.

In a particular embodiment, the catalytic conversion of oxygenate comprises more than 50 wt.%, preferably at least 65 wt.%, in the calculation of the total weight of molecular sieve in the catalyst of the conversion of oxygenate, one-dimensional molecular sieve having 10-membered ring channels.

In one of the embodiments of the invention in the catalytic conversion of oxygenate use of molecular sieves in the hydrogen form, e.g., HZSM-22, HZSM-23, and HZSM-48, HZSM-5. Preferably at least 50 wt.%, more preferably at least 90 wt.%, even more preferably, at least 95 wt.% and most preferably 100% of the total number of the used molecular sieve is in the hydrogen form. When molecular sieves are obtained in the presence of organic cations, the molecular sieve may be activated by heating in an inert or oxidative atmosphere to remove the organic cations, for example, by heating at temperatures above 500°C for 1 hour or more. The zeolite is usually obtained in the sodium or potassium form. The hydrogen form can then be obtained by the operation of ion exchange with ammonium salts followed by another heat treatment, for example, in an inert or oxidizing atmosphere at temperatures above 500°C for 1 Casali more. Molecular sieves obtained after ion exchange, also referred to as ammonium form.

Molecular sieve can be used as such or in the form of a composition, such as a mixture or combination of the so-called binder and/or filler material, and optionally also with the active component of the matrix. Other components may also be present in the composition. If they use one or more molecular sieves such as, in particular, when there are no binders, filler or active matrix material, then the molecular sieve itself is called a catalyst for conversion of oxygenates. In the formulation of a molecular sieve in combination with other components of the mixture, such as a binder and/or filler material, called a catalyst for conversion of oxygenates.

It is desirable to use a catalyst having good mechanical strength or the crushing strength, as in an industrial environment the catalyst is often subjected to harsh transportation, in which the catalyst is broken down to powder form. The latter causes problems during processing. Preferably molecular sieve, therefore, is introduced into a binder. Examples of suitable materials in the formulation include active and inactive materials and synthetic or natural zeolites, as well as reorganize�Kie materials, such as clay, silica, alumina, silica-alumina, titanium oxide, zirconium dioxide and aluminosilicates. For the purposes of the present invention, the preferred inert materials with low acidity such as silica, as they can prevent unwanted side reactions that can occur in the case of a more acidic material, such as alumina or silica-alumina.

Typically, the catalytic conversion of oxygenates deactivated during the process. Can be used traditional technology of regeneration of the catalyst. The catalyst particles used in the process of the present invention may have any shape known to specialists in this field and suitable for this purpose, for example, it may be present in the form of catalyst particles spray-dried, pellets, tablets, rings, extrudates, etc. Extruded catalysts may be given a different configuration, such as cylindrical and trehdolchatye. If desired, the spent catalyst for conversion of oxygenates may be recovered and sent for recycling in the process according to the invention. Particle spray drying, allowing the use of a fluidized bed or water separation system of the reactor, are preferred.

In spray drying usually get spherical particles. Preferably the average particle size is in the range of 1-200 microns, preferably 50-100 microns.

A preferred variant of the implementation stage (b), described above, is preferably carried out in the area of General relativity, including pseudovirions layer or flexible layer, for example, bistrogaelic layer or water separation system of the reactor, although, in General, for the process of General relativity, especially for the MTP process, can also be used in the reactor fixed bed or tubular reactor. Can be applied in the system of sequential reactors.

In one of the embodiments of the invention, the zone of General relativity involves many sequential reaction sections. The oxygenate may be filed, at least two sequential reaction section.

When using multiple reaction zones, concomitant olefin feedstock serves primarily as a part of simple enriched dimethylethylene ether raw materials, which takes place in the first reaction zone.

The preferred molar ratio of oxygenate in oxygendemand feedstock to the olefin in the olefin accompanying raw materials supplied to the OTO conversion zone, used depends on the specific oxygenate and the number of reaction connected by oxygen of the alkyl groups therein. Before�occhialino molar ratio of oxygenate to olefin in the total raw material is in the range from 20:1 to 1:10, more preferably in the range from 18:1 to 1:5 and more preferably in the range from 15:1 to 1:3.

In the area of General relativity can also be administered the diluent mixed with the oxygenate and/or secondary raw materials, if present, or separately. The preferred diluent is steam, although it can also be used with other inert diluents. In one of the embodiments of the invention the molar ratio of oxygenate to diluent is between 10:1 and 1:10, preferably between 4:1 and 1:2, most preferably between 3:1 and 1:1, e.g. 1.5:1, especially when the oxygenate is methanol and the diluent is water (steam).

Raw materials containing ethane, for stage (a) of the first method of producing olefins according to the invention can be any ethane feedstock. Regarding including ethane feedstock in the present paper, fresh raw materials fed into the process before entering the cracking zone and comprising ethane, may be combined with one or more circulating technology flows generated either in the cracking zone or in the zone of General relativity or to provide any other raw material origin in the process. In addition to ethane, ethane feedstock may also include higher paraffins such as propane and butanes. Preferably comprising ethane feedstock comprises in the range from 50 to 100 mol.% ethane, more preferably 80-99 mol.% ethane, based on the total number of moles including ethane feedstock.

Preferably ethane feedstock derived from natural gas or associated gas.

Oxygendemand raw materials entering into stage (b) of the first process of producing olefins according to the invention, can be any comprising an oxygenate feedstock. Oxygendemand raw material includes at least methanol and/or DME, obtained when the flow of hydrogen from the combined effluent stream and a feed containing carbon monoxide and/or carbon dioxide, in the area of synthesis of oxygenates and the conversion of hydrogen and carbon monoxide and/or carbon dioxide to methanol and/or a simple dimethyl ether. Oxygendemand raw material may further include oxygenates, such as, for example, other alcohols, other ethers, aldehydes, ketones and esters. Preferably oxygendemand includes raw water as diluent. Oxygendemand raw materials may include compounds other than water and oxygenates.

In one of the embodiments of the invention, the oxygenate is obtained as the reaction product synthesis gas. The synthesis gas may, for example, be formed from fossil fuels such as natural gas or oil, or obtained in the process of coal gasification. Suitable processes for this purpose are, for example, processes, Russ�trannie in the book of Industrial Organic Chemistry, Klaus Weissermehl and Hans-Jürgen Arpe, 3rdedition, Wiley, 1997, pages 13-28. This book also considers the production of methanol from synthesis gas on pages 28-30.

In another embodiment, the oxygenate is obtained from biomaterials, such as fermentation products. For example, a method described in DE-A-10043644.

Oxygendemand raw materials can be sent directly from one or more zones of the synthesis of oxygenates, however, it can also be obtained from a Central repository of oxygenates.

Olefin related raw materials, not necessarily submitted with oxygendemanding feedstock to the OTO conversion zone may be a single olefin or mixture of olefins. In addition to olefins, concomitant olefin feedstock may contain other hydrocarbon compounds, such as, for example, paraffin, alkyl, aromatic compounds or a mixture thereof. Preferably concomitant olefin feedstock comprises more than 20 wt.% olefin fraction, more preferably more than 25 wt.%, also more preferably more than 50 wt.%, moreover, the olefin fraction is composed of olefin(s). Olefin accompanying the raw materials can consist essentially of the olefin(s).

Any olefin compounds in olefin accompanying raw materials are preferably paraffinic compounds. If concomitant olefin raw material contents�t not any olefinic hydrocarbon compound, it is preferably a paraffin compound. These paraffinic compounds are preferably contained in an amount in the range of 0 to 80 wt.%, more preferably in the range from 0 to 75 wt.%, also more preferably in the range from 0 to 50 wt.%.

Under unsaturated compounds refers to organic compounds containing at least two carbon atoms, connected double or triple bond. Under olefin refers to an organic compound containing at least two carbon atoms connected by a double bond. The olefin may be monoolefins containing one double bond, or a polyolefin containing two or more double bonds. Preferably, the olefins contained in concomitant olefin feedstock are monoolefins. C4 olefins, also called butenes (1-butene, 2-butene, ISO-butene and/or butadiene), especially the C4 monoolefins, are preferred compounds in concomitant olefin raw material.

Preferred olefins contain from 2 to 12, preferably from 3 to 10 and more preferably 4 to 8 carbon atoms.

Examples of suitable olefins that may be contained in concomitant olefin feedstock include Eten, propene, butene (one or more of 1-butene, 2-butene and/or ISO-butene (2-methyl-1-propene)), Pantin (one or more 1-penten, 2-penten, 2-me�Il-1-butene, 2-methyl-2-butene, 3-methyl-1-butene and/or cyclopentane), hexene (one or more 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-penten, 2-methyl-2-penten, 3-methyl-1-penten, 3-methyl-2-penten, 4-methyl-1-penten, 4-methyl-2-penten, 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, 3,3-dimethyl-1-butene, Methylcyclopentane and/or cyclohexene), heptane, octane, nonane and deceny. The preference for a specific olefins in the olefin accompanying raw materials may depend on the objectives of the process, such as preferred obtaining ethylene or propylene.

In a preferred embodiment the concomitant olefin feedstock preferably contains olefins containing 4 or more carbon atoms (i.e. C4-olefins), such as butenes, pentene, hexene and Heptene. More preferably, the olefin fraction concomitant olefin feedstock comprises at least 50 wt.% of butenes and/or pentanol, even more preferably at least 50 wt.% of butenes and most preferably at least 90 wt.% of butenes. A butene may be 1-, 2 - or ISO-butene or a mixture of two or more of them.

Preferably, at least part oxygenating raw material is obtained by conversion of methane into synthesis gas and the supply of the synthesis gas in the area of synthesis of oxygenates for the synthesis of oxygenates. The methane is preferably derived from natural gas or associated gas, more preferably in superdrag gas or associated gas, from where obtained include ethane feedstock. Benzene used for the conversion of ethylene to ethylbenzene, can be any available benzene. Benzene may be benzene, obtained in stage (a) of the method according to the invention. As disclosed in U.S. patent 6677496, the process of cracking of ethane is usually accompanied by a receipt, up to 0.6 wt.% benzene, based on the total number of ethane feedstock. However, benzene can also be obtained from any other source.

Preferably, the benzene produced from higher hydrocarbons such as propane and butane, more preferably from propane and butane, obtained as a condensate or LPG from natural gas or associated gas, even more preferably of the same natural gas or associated gas, which is obtained include ethane feedstock.

Raw materials, including methane and ethane, is fed to a second process of producing olefins according to the invention can be any feedstock comprising methane and ethane. Preferably, the feedstock comprising methane and ethane is a natural gas or associated gas.

Preferably, the feedstock comprising methane and ethane, includes in the range of from 1 to 20 mol.% ethane, based on the total weight of raw materials.

In another aspect, the invention relates to a combined system for obtaining olefins, wherein the system includes

a) a steam cracking system having one or Bo�it includes entries for ethane feedstock and steam, and conclusion emerging from the cracking installation of the stream comprising olefins and hydrogen;

(b) a system for the conversion of an oxygenate-to-olefin having one or more inlets for receiving oxygenating raw material, and comprising a reaction zone to contact oxygenating feedstock with a catalyst for conversion of oxygenate in the conditions of the oxygenate conversion, and output to the outgoing flow from the zone of conversion of an oxygenate-to-olefin comprising olefins;

(C) processing system designed to receive at least part of the effluent from the cracking installation of the flow and at least part of the effluent from the zone of conversion of an oxygenate-to-olefin stream to obtain a merged exhaust stream, the processing section includes a separation system, an outlet for flow of the olefin product and an outlet for hydrogen;

(d) the system of synthesis of oxygenate that has one or more inlets for raw material, containing carbon monoxide and/or carbon dioxide, and enter for hydrogen and o for oxygenating raw materials; and

means for supplying hydrogen from the output from the processing section to enter the hydrogen system of the oxygenate synthesis.

Optional hydrogen from the combined stream is mixed with the raw material containing carbon monoxide and carbon dioxide, before it is fed into the synthesis system of the oxygenate. In this case, the inputs for the raw material containing the oxide operadi/or carbon dioxide, and enter to hydrogen system of the oxygenate synthesis may be the same type.

In case there is another aspect, the invention relates to the use of hydrogen obtained from the process of cracking of ethane to ethylene with getting oxygenating raw materials for the process of conversion of an oxygenate-to-olefin.

Figure 1 is a diagram of one of the embodiments of the invention in the part of the United system for obtaining olefins according to the invention. In the system of figure 1 comprising ethane feedstock and steam is fed via lines 1 and 3 respectively in the system 5 steam cracking, including cracking zone for ethane steam cracking to ethylene. From the system 5 steam cracking effluent from the cracking zone, the stream is removed via line 7.

Figure 1 raw materials containing carbon monoxide and/or carbon dioxide, for example, synthesis gas, also passes through line 9 to system 11 synthesis of oxygenate that includes the area of the oxygenate synthesis for the formation of oxygenates from hydrogen and at least one of carbon monoxide and/or carbon dioxide. From the system 11 synthesis of oxygenate oxygendemand raw materials is removed via line 13. Oxygendemand raw material is fed into a system 15 the conversion of the oxygenate-to-olefins, comprising the OTO area for the conversion of oxygenates to lower olefins, e.g., ethylene and propylene. Not necessarily concomitant olefin feedstock (not shown) serves to �the system 15 the conversion of an oxygenate-to-olefins together with oxygendemanding raw materials. From the system 15 the conversion of an oxygenate-to-olefins effluent from the zone GRT stream passes via line 17.

Emerging from the cracking zone, the flow in and out of the zone GRT stream are combined in the combined effluent via line 19 and sent to the processing section 21. The processing section 21 includes at least a separator system for separating hydrogen from the combined effluent stream and for separating ethylene from the combined exhaust stream. Hydrogen is removed from section 21 of the processing and is directed through line 23 to the line 9 and is mixed with the synthesis gas. Ethylene is withdrawn separately from section 21 of the processing and fed via line 25 to the system 27 oxidation of ethylene via line 29. From the system 27 ethylene oxide ethylene oxide is withdrawn via line 31 and is supplied to the system 33 hydrolysis of ethylene oxide, which includes the zone of hydrolysis of ethylene oxide, where the hydrolyzed ethylene oxide to MEG. Water is injected into the system 33 hydrolysis of ethylene oxide by the line 35. System 27 ethylene oxide and the system 33 hydrolysis of ethylene oxide, form a system of 37 synthesis of MEG. From the system 37 synthesis MEG effluent, including MEG, is withdrawn via line 39, and carbon dioxide via line 41.

Examples

The invention is illustrated by the following not limiting the substance and scope of the claims examples of calculation.

Example 1

In the examples, a comparison of several embodiments of the present invent�tion with the comparative examples using model calculations. As a basis for examples 1A-g model taken joint trial GRT/cracking of ethane. Table 1 presents an overview of the input raw materials and the estimated yields of products.

Calculations made using the Spyro model for the simulation of cracking process, combined with the patented model for modeling the conversion of General relativity. Key input for the models was as follows.

Cracking

The ratio of steam to ethane was 0.35 wt.%. USC spiral used for calculations Spyro. The design pressure at the outlet of the spiral was equal to 1.77 bar absolute value, and the conversion of ethane 65% and residence time of 0.24 seconds.

The OTO conversion

MeOH 5012 dpi filed in the OTO reactor with 1384 t/d circulating and superheated steam and 1775 t/d circulating stream C4. The model was calibrated for small-scale experiments conducted to determine the distributions of the products in the single pass conversion of General relativity. Components are fed into the OTO reactor, evaporated and heated so that the temperature in the reactor was maintained between 550-600°C. the pressure in the reactor was 2 bar absolute values. The OTO catalyst was Origen in the reaction medium under conditions when the mass hourly space velocity (WHSV) was 4-10 h-1where WHSV is defined as the total mass flow of the raw material above the mass of catalyst per hour. Were used followed by�s catalysts: the composition and preparation: a 32 wt.% ZSM-23 SAR 46, 8 wt.% ZSM-5 SAR 280, 36 wt.% kaolin, 24 wt.% Zola silicon dioxide and after calcination of the ammonium form of the particles of the spray drying, 1.5 wt.% R was introduced by impregnation of H3PO4. The catalyst was again calcined at 550°C. the Steam and circulating flows C4 excluded from the tables on the composition of the products.

Methanol is sent to the OTO process (approximately 5000 t/d, see table 1) were synthesized using at least part of the hydrogen from the combined stream.

Raw materials containing carbon monoxide and/or carbon dioxide, obtained by combining the synthesis gas obtained from one or more processes for producing synthesis gas and optionally flow of carbon dioxide obtained during the synthesis of MEG. The outputs of methane was calculated by the Aspen model. To maintain the concentration of inert materials at about 40 wt.% in the circulating synthesis gas, a regulated amount of fresh stream with a circulating line.

Hydrogen from the combined effluent stream and carbon dioxide from synthesis MEG is taken as pure 99.9+%.

The concentration of natural gas amounted to 94.3 mol.% CH4For 0.6 mol.% With2N6That is 4.6 mol.% N2And 0.4 mol.% CO2and 0.1 mol.% Ar, based on the total number of moles in the flow of natural gas.

Used synthesis gases were as follows:

- The synthesis gas from the catalytic part�tion oxidation of natural gas (gasification company Shell). The SGP syngas included to 61.2 mol.% hydrogen 34,0 mol.% carbon monoxide, a 2.1 mol.% carbon dioxide and 2.5 mol.% inert gas (N2, Ar and CH4), based on the total number of moles in the SGP syngas.

- The synthesis gas from the process Autoterminal reforming of natural gas (ATR). ATR syngas consisted of 65.5 mol.% hydrogen, of 26.7 mol.% carbon monoxide, a 6.4 mol.% of carbon dioxide and 1.7 mol.% inert gas (N2, Ar and CH4), based on the total number of moles in the ATR syngas.

- A mixture of synthesis gas from steam reforming of methane (SMR) and SGP synthesis gas. The mixture included 65,8 mol.% hydrogen, to 25.6 mol.% carbon oxide, 4,4 mol.% carbon dioxide and 3.8 mol.% inert gas (N2, Ar and CH4), based on the total number of moles in the mixture of Mingazov.

Table 2A provides an overview of the raw materials, i.e. hydrogen from the combined effluent stream, and a feed containing carbon monoxide and/or carbon dioxide sent to the methanol synthesis process.

In table 2b presents an overview of the composition of the raw material sent to the methanol synthesis process.

Table 3 presents an overview of raw materials, i.e. natural gas, oxygen and water necessary for producing synthesis gas.

Table 4 shows the production of methanol based on the waste carbon dioxide.

Experiment 1A: (not invention)

Methanol feedstock to the OTO process synthesized from a mixture of SGP and SMR Synthe�gas. Required 2949 tons/day of natural gas for a sufficient amount of methanol.

Experiment 1b:

Methanol feedstock to the OTO process synthesized from a mixture of parts of hydrogen from the combined effluent stream and SGP synthesis gas. When the supply of hydrogen from the combined effluent stream to the methanol synthesis process, natural gas consumption for the production of methanol is reduced to 8 wt.% in the calculation of natural gas required for producing methanol in experiment 1A. There is no need to add additional SMR synthesis gas. In addition, without the use of SMR synthesis gas, can significantly reduce water consumption, in principle, water is not used for producing synthesis gas.

In addition, the concentration of inert gases (N2, Ar and CH4) in raw materials for the synthesis of methanol is reduced compared to the levels observed in experiment 1A, due to the dilution SGP synthesis gas with hydrogen, obtained from the cracking installation of ethane.

Experiment 1C:

Methanol feedstock to the OTO process synthesized from a mixture of hydrogen from the combined effluent stream and SGP synthesis gas. In addition, added pure carbon dioxide from a plant producing MEG with increasing carbon dioxide content up to 3.3 mol.% in the calculation of all raw materials for the synthesis of methanol. The consumption of natural gas for producing methanol lowered�subscribe to 12 wt.% in the calculation of natural gas required for the production of methanol in experiment 1A. In addition, receive a 255 ton/day of methanol-based extract of carbon dioxide, i.e. carbon dioxide, formed as part of the process for producing synthesis gas, which would require its separation or binding in any other way, and storage. As a result, decreased penalties for carbon dioxide in the process.

And here, further decreased the concentration of inert gases (N2, Ar and CH4).

Experiment 1d:

Methanol feedstock to the OTO process synthesized from a mixture of hydrogen from the combined effluent stream, SGP synthesis gas and with the addition of additional hydrogen, for example, from the second or additional cracking installation of ethane or installation for the production of styrene. In addition, added pure carbon dioxide from a plant producing MEG with increasing carbon dioxide content to 7.9 mol.% in the calculation of all raw materials for the synthesis of methanol. The consumption of natural gas for production of methanol decreased by 27 wt.% in the calculation of natural gas required for producing methanol in experiment 1A. In addition, receive 1062 tons/day of methanol based on the waste carbon dioxide.

And here, further decreased the concentration of inert gases (N2, Ar and CH4).

Experiment 1E:

Methanol feedstock for the process Of�About synthesized from a mixture of parts of hydrogen from the combined effluent stream and ATR synthesis gas. When the supply of hydrogen from the combined effluent stream to the methanol synthesis process, natural gas consumption for the production of methanol decreased compared with experiment 1A. The consumption of natural gas for production of methanol decreased by 1 wt.% in the calculation of natural gas required for producing methanol in experiment 1A. You no longer need to add additional SMR synthesis gas.

In addition, decreased the concentration of inert gases (N2, Ar and CH4) in raw materials for the synthesis of methanol compared to the levels observed in experiment 1A, due to the dilution ATR synthesis gas with hydrogen, obtained from the cracker ethane.

Experiment 1f:

Methanol feedstock to the OTO process synthesized from a mixture of parts of hydrogen from the combined effluent stream and ATR synthesis gas. In addition, added pure carbon dioxide from a plant producing MEG with increasing carbon dioxide content to 7.1 mol.% in the calculation of all raw materials for the synthesis of methanol. The consumption of natural gas for production of methanol decreased by 6 wt.% in the calculation of natural gas required for producing methanol in experiment 1A. In addition, receive a 273 tons/day of methanol based on the waste carbon dioxide. As a result, decreased penalties for carbon dioxide in the process.

And here, further reduced�camping in the concentration of inert gases (N 2, Ar and CH4).

Experiment 1g:

Methanol feedstock to the OTO process synthesized from a mixture of almost all the hydrogen from the combined effluent stream and ATR synthesis gas. In addition, added pure carbon dioxide from a plant producing MEG with increasing carbon dioxide content to 7.9 mol.% in the calculation of all raw materials for the synthesis of methanol. The consumption of natural gas for production of methanol decreased by 9 wt.% in the calculation of natural gas required for producing methanol in experiment 1A. In addition, received 443 tons/day of methanol based on the waste carbon dioxide. As a result, decreased penalties for carbon dioxide in the process.

And here, further decreased the concentration of inert gases (N2, Ar and CH4).

When using synthesis gas, such as SGP synthesis gas, which includes relatively small amounts of carbon dioxide can bind significant amounts of waste carbon dioxide in the form of methanol, ethylene or products formed by them. In addition, when using synthesis gas obtained in the process, which in principle is not formed or formed little water, such as process non-catalytic partial oxidation, the flow rate in�s is significantly reduced.

1. A method of producing olefins, comprising
(a) steam cracking comprising ethane feedstock in the cracking zone and the cracking conditions with obtaining leaving the cracking zone of a stream comprising at least olefins and hydrogen;
(b) conversion oxygenating raw material in the conversion zone of the oxygenate-to-olefins in the presence of a catalyst with the receipt coming out from the zone of oxygenate to olefins (OTO) flow of at least olefins and hydrogen;
(c) combining at least part of the effluent from the cracking zone flow and parts coming out of the area by the stream with obtaining a combined effluent stream; and
d) separation of hydrogen from the combined effluent stream, forming at least part oxygenating raw material by supplying hydrogen of step (d), and raw materials containing carbon monoxide and/or carbon dioxide, in the area of synthesis of oxygenates and receipt of oxygenates.

2. A method according to claim 1, wherein the olefins obtained in stage a) and/or (b) include ethylene and propylene.

3. A method according to claim 1 or 2, comprising feeding hydrogen and at least one of carbon monoxide and carbon dioxide in the area of synthesis of oxygenates in a molar ratio in the range from 2.0 to 3.0.

4. A method according to claim 1 or 2, comprising feeding hydrogen and at least one of carbon monoxide and carbon dioxide in the area of synthesis of oxygenates in molar Rel�tion in the range from 2.0 to 2.2.

5. A method according to claim 1, wherein the raw material containing carbon monoxide and/or carbon dioxide, includes the syngas, preferably synthesis gas with a molar ratio of hydrogen to carbon monoxide and/or carbon dioxide in the range from 1.1 to 1.9, more preferably from 1.3 to 1.8.

6. A method according to claim 1, wherein the raw material containing carbon monoxide and/or carbon dioxide comprises carbon dioxide, obtained from underground natural gas or oil formation.

7. A method according to claim 1, wherein the raw material containing carbon monoxide and/or carbon dioxide comprises carbon dioxide, obtained from the process of producing ethylene oxide and/or monoethylene glycol.

8. Combined system for producing olefins, wherein the system includes
a) a steam cracking system having one or more inlets for including ethane feedstock and steam and an outlet for exiting the cracking installation of the stream comprising olefins and hydrogen;
(b) a system for the conversion of an oxygenate-to-olefins having one or more inlets for receiving oxygenating feedstock, and comprising a reaction zone to contact oxygenating feedstock with a catalyst for conversion of oxygenates in terms of conversion of oxygenates, and the output coming out of the process of conversion of an oxygenate-to-olefins stream comprising olefins;
c) processing system set for reception by m�Nisha least part of the coming out process of conversion of an oxygenate-to-olefins stream to obtain a merged exhaust stream, the processing section includes a separation system, an outlet for flow of the olefin product and an outlet for hydrogen;
(d) a system for the synthesis of oxygenates, having one or more inlets for raw material, containing carbon monoxide and/or carbon dioxide, and enter for hydrogen and o for oxygenating feedstock; and means for supplying hydrogen from the outlet for hydrogen of the section to be processed in the input hydrogen synthesis of oxygenates.



 

Same patents:

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1 dwg, 1 ex

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1 dwg, 1 tbl

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2 cl, 1 dwg, 2 tbl

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13 cl, 6 ex, 1 dwg

FIELD: chemistry.

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3 cl, 1 ex, 2 tbl, 3 dwg

FIELD: production of marine fuels by high vacuum distillation of mazut, light thermal cracking of vacuum gas oils and oxidation of heavy tar oils; oil refining industry.

SUBSTANCE: proposed method is used for production of light marine fuel, high-viscosity light marine fuel and low-viscosity marine fuel. Light marine fuel and high-viscosity light marine fuel are used in marine power export plants according to international standard for marine fuels MS ISO/DIS-F-8217 and for export delivery. Proposed method consists in extraction of fractions by means of atmospheric-vacuum distillation followed by light thermal cracking of vacuum gas oils and blending of these fractions. According to proposed method, fractions of temperature of 180-360°C at initial-boiling point of 400°C and end-boiling point of 400°C. For production of light marine fuel and/or marine high-viscosity light fuel, fraction of heavy vacuum gas oil at final-boiling point of 400°C or mixture of this fraction with fraction of light vacuum gas oil at initial-boiling point of 400°C is subjected to light thermal cracking followed by fractionating and separation of light fraction and residual fractions of secondary distillates at temperature of 200-400°C and final-boiling point of 400°C. Then, these fractions are blended in balance relation, thus producing marine high-viscosity fuel (wide fraction at boiling point higher than 200°C) or at ratio of 50:50 for producing light marine fuel and/or marine low-viscosity fuel additionally entrapping the fraction of light vacuum gas oil at initial-boiling point of 400°C observing the following ratio of components: 45:45:10-40:40:20, respectively. For obtaining marine low-viscosity fuel, part of fraction of light vacuum gas oil at initial-boiling point of 400°C (up to 70%) blended with balance amount of fraction of heavy vacuum gas oil at end-boiling point of 400°C is first subjected to light thermal cracking accompanied by separation of light gas oil at 200-400°C, after which the secondary distillate thus obtained is blended with remaining part of fraction of light vacuum gas oil at initial-boiling point of 400°C (up to 30%) and straight-run diesel fraction at 180-360°C at ratio of 20:50:20 mass-%. Subjected to light thermal cracking is either fraction of heavy vacuum gas oil at final-boiling point of 400°C and at final-boiling point not exceeding 500-560°C due to unfavorable action of high-boiling fractions on quality of products or mixture of fractions of light and heavy vacuum gas oils at initial-boiling point of 400°C and final-boiling point of 400°C at balance ratio or at ratio of 20:80 at separation of secondary distillates at 200-400°C and residue at end-boiling point of 400°C which are basic components of marine high-viscosity fuel, marine light fuel and marine low-viscosity fuel.

EFFECT: low content of high-molecular hydrocarbons; reduced viscosity; enhanced fluidity and pumpability; low congelation point.

4 cl, 1 dwg, 6 tbl, 9 ex

The invention relates to a method for producing high quality coke delayed coking
The invention relates to methods of processing and recycling of waste oil accumulated in the form of sludge, and may find application in the oil refining and petrochemical industry

The invention relates to the extraction and removal of by-products, representing a multi-core aromatic organic compounds from a stream of steam flowing from the reaction zone dehydrogenization normally gaseous hydrocarbon
The invention relates to chemical processing of petroleum products, namely the process of obtaining trademark of gasoline with O. H. 76-PM and organic gasoline with O. H. 92 - EM and benzene highest purification of catalization reforming wide gasoline fractions

The invention relates to methods of producing fuel for marine engines and can be used in the refining industry

FIELD: chemistry.

SUBSTANCE: invention relates to the catalytic conversion of a renewable raw material - products of the biomass fermentation (ethanol, fusel alcohols) and their mixtures with vegetable oil into an alkane-aromatic fraction C3-C11+, which can be used for obtaining fuel components. The method of obtaining alkane and aromatic hydrocarbons from the products of the biomass processing for obtaining the hydrocarbon fuel components includes passing the products of the biomass processing through a layer of a preliminarily regenerated zeolite ZSM-based catalyst, containing Pd and Zn, in an inert atmosphere at an increased temperature. The method is characterised by the fact that as the catalyst used is the Pd-Zn/ZSM/Al2O3 catalyst of the general formula of 0.6 wt % Pd-1 Zn/Al2O3/ZSM, with the products of the biomass processing, which contain a mixture of organic fermentation products or fusel alcohols, being passed through the catalyst layer at a temperature of 280-500°C and volume rate of 0.3-6 h-1.

EFFECT: extension of the raw material base and method for obtaining alkane and aromatic hydrocarbons.

5 cl, 6 tbl, 26 ex

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