Catalyst and method for synthesis of alkane-olefin hydrocarbons in presence of said catalyst

FIELD: chemistry.

SUBSTANCE: invention relates to heterogeneous catalytic conversion of organic compounds, specifically to catalytic conversion of a mixture of aliphatic alcohols to a mixture of alkane-olefin hydrocarbons, particularly C5-C8 hydrocarbons. Described is catalyst for synthesis of alkane-olefin hydrocarbons based on γ-aluminium oxide, distinguished by that, the catalyst contains tungsten oxide and rhenium oxide with the following ratio of components, in wt %: tungsten oxide 1.2-6.7; rhenium oxide 0-1.3; γ-aluminium oxide - the rest. Described also is a method for synthesis of alkane-olefin hydrocarbons with an even or combined even and odd number of carbon atoms through cross-coupling reaction of ethanol or its mixture with aliphatic alcohols in the presence of the said catalyst.

EFFECT: described catalyst enables to increase output of C5-C8 olefin-alkane fractions to 45% and reduce output of gaseous C1-C2 products to 30-35% with 85-95% conversion of initial alcohols.

5 cl, 5 tbl, 3 dwg, 9 ex

 

The invention relates to the field of heterogeneous-catalytic transformations of organic compounds, namely the catalytic conversion of mixtures of aliphatic alcohols in the mixture of hydrocarbons alkane-olefin series, in particular With5-C8hydrocarbons, which are effective additives for hydrocarbon fuels for various purposes.

The beginning of the XXI century, many experts characterize as the end of the era of cheap oil. Due to the growing energy needs of mankind we have to look for alternative fuels. Alternative include substances that can be used in internal combustion engines or power plants instead of fuels of oil origin. The most popular currently got the engines running on nonrenewable fuels - gasoline, diesel fuel, natural gas. It is estimated at least before 2030 humanity will use hydrocarbon fuels in internal combustion engines as the primary [1]. Oil and natural gas is not crumbling, and their extraction and processing have a tendency appreciation. In addition, these fuels pollute the environment sulfur, nitrogen and aromatic compounds, and therefore accepts all the new rules on the content of these elements in the top of the willow (Euro 1, 2, 3..). This greatly increases their value.

In recent years, the attention of researchers around the world are drawn to alcohol fuels, their advantages and disadvantages when used in internal combustion engines. In this regard, the most prevalent found lower aliphatic alcohols: methanol and ethanol, while higher alcohols are considered as stabilizing additives.

It should be noted that hydrocarbon fuels will prevail, at least until 2050 In this context, alternative approaches of obtaining aliphatic hydrocarbons as high quality components fuels is of particular importance.

Thus, it is possible to use ethanol as raw material for production of synthetic gasoline or high-octane components: alkylaromatic hydrocarbons and alkanes, isotrate, and the resulting fuel is environmentally friendly due to the lack of sulfur and nitrogen.

It should be emphasized that due to increasingly stringent environmental requirements for road transport, alkane-olefin fraction is the most valuable, because it provides a greater degree of environmental acceptability of fuel.

Known zeolite catalyst HZSM-5 with Si/Al=30 manufactured by CJSC nijega omskie sorbents", translated in the H-form in accordance with the methodology proposed in [2], in the presence of which spend one of the most promising ways of obtaining hydrocarbon components of the fuel by ethanol processing described in [3]. According to this method, the products of the conversion of ethyl alcohol are gaseous fraction containing saturated and unsaturated hydrocarbons, C1-C4, liquid hydrocarbon fraction and the water.

Study of catalytic conversion of ethanol is carried out in a laboratory setup flow-type fixed bed of the catalyst at T=300-400°C, P=1-6 ATM, volumetric flow rates of ethanol WC2H5OH=2500-5000 h-1. Loading of the catalyst with a particle size of 0.2-0.5 mm is 1 herebasically treatment of the zeolite is in the calcination of the sample at T=500°C for 1 h in a stream of nitrogen.

The maximum yield of liquid hydrocarbon fraction is 18%. The liquid hydrocarbon fraction composed of saturated and unsaturated hydrocarbons, cycloalkanes and alkyl substituted compounds of the aromatic series.

The disadvantages of this method include high gas and high content of aromatic compounds in the liquid product, where the number reaches more than 60 wt.%.

Known catalytic component is ice, containing the hydride phase zhelezorudnogo of intermetallic compound of General formula: Ti1-xFe1-yMzHnwhere M is one or more metals of IV-VII groups; a lanthanide or a mixture in the form of mischmetall; x=0-0,3; y=0-0,7; z=0-0,7; n>0 [4], preferably [TiFeof 0.95Zr0,03Mo0,02]H2or [TiFeof 0.95Mn0,03Cr0,02]H2and industrial aluminium oxide-platinum (AP-56, AP-64) or ecumenically catalyst when the mass ratio of the industrial catalyst to the intermetallic compound is 1:10.

The disadvantages of the described compositions include the low chemical and mechanical stability of intermetallic compounds, which quickly become brittle and destroyed.

In the presence of the described catalyst compositions provide a method of obtaining a8or10hydrocarbons, mostly dimethylamino, aliphatic alcohol, which is used as Isobutanol or isopentanol, in an inert gas environment at a temperature of 300-420°C, a pressure of 30-80 bar and a flow rate of 0.1-0.8 h-1.

According to the procedure described in the products of transformation of the corresponding aliphatic alcohols are gaseous fraction containing saturated hydrocarbon, C1-C4, liquid hydrocarbon fraction and water. Liquid hydrocarbon fraction with the contains up to 50% alkanovykh products of dimerization of the carbon skeleton of alcohol, 10-15% of oxygen-containing compounds.

In the presence of catalytic compositions described in the previous work, carry out a method of obtaining alanovoy fraction4-C16mainly isotrate of ethanol in an inert gas environment at a temperature of 300-420°C, a pressure of 30-80 bar and a flow rate of 0.2-0.8 h-1[5]. This method is the closest to the essence and we have chosen for the prototype.

The disadvantages of the above method include high gas (60-70%, containing mainly methane), the low yield of the reaction products, namely5-C810-20%, and also the drawback of the catalyst is low chemical and mechanical stability of intermetallic compounds, which quickly becomes brittle and destroyed.

The present invention is to create a catalyst and the development of a method of converting ethanol or mixtures thereof with aliphatic alcohols, hydrocarbons alkangovolo and olefin series to increase the output alkanovykh hydrocarbons, namely fraction5-C8and the reduction of the yield of gaseous products.

This task is solved in that the proposed catalyst receiving alkane-olefinic hydrocarbons based on γ-alumina, characterized in that it contains an oxide of tungsten and an oxide of rhenium, with the following sootnoshenie the components, wt.%:

tungsten1,2-6,7
the rhenium oxide0-1,3
γ-aluminarest

The problem is solved also by the fact that the method for obtaining alkane-olefinic hydrocarbons with an even or joint adjacent odd and even numbers of carbon atoms by reaction cross-condensation of ethanol or mixtures thereof with aliphatic alcohols in the presence of the above catalyst.

The reaction cross-condensation is carried out at a temperature of 320-380°C, the inert gas pressure of 1-5 MPa at a feed rate of the mixture of aliphatic alcohols on the catalyst mainly 0,6 DM3/h·DM3cat., and as the aliphatic alcohols used or butanol, or propanol, or ISO-amyl alcohol, taken in an amount up to 40 wt.%, with respect to ethanol. The catalyst pre-thermoablative at a temperature of 450°C in a stream of hydrogen for 10 hours.

The reaction cross-condensation is the formation of hydrocarbon skeleton of a mixture of alcohols of different nature in the process of their rehabilitation dehydration.

Thus, the authors of the present invention were carried out to study fo the formation of the hydrocarbon skeleton of the cyclic compounds by reductive dehydration of ethanol and Cyclopentanol [6]. But the purpose of obtaining alkanovykh and olefinic hydrocarbons from ethanol in a mixture with aliphatic alcohols the reaction is used for the first time.

In the same paper it is shown that in the presence of metal oxide catalysts for the esterification reaction and homogenization are the main routes of catalytic transformations of aliphatic alcohols With2-C5. In the course of these reactions are formed mainly of oxygen-containing products: ethers, esters, aldehydes, ketones, acetals, and aliphatic alcohols containing more carbon atoms in the hydrocarbon chain of the skeleton compared to the original reactants.

It should be noted that the proposed catalyst containing as the active component solid solution of oxides of rhenium and tungsten deposited on the surface of γ-Al2O3when found optimal conditions provides along with the above processes, the intensive course of the condensation reaction of the carbon skeleton of the aliphatic alcohols to form alkane-olefin fraction, as well as the redistribution of hydrogen produced during the process [7].

Stability and high activity of the tungsten-rhenium catalyst in contrast to W can be explained by the formation of a mixed oxide, representing the solid dissolve the rhenium oxide of tungsten, in all likelihood, provide the necessary acid-base properties, providing high selectivity of the cross-condensation of the carbon skeleton of the spirits.

The following examples illustrate the present invention but in no way limit its scope.

Preparation of catalyst

Anodic dissolution of tungsten and rhenium in methanol

Getting alkoxide complexes of tungsten and rhenium in methanol, which are the precursors of the active components, carried out by the method of electrochemical dissolution of metals in methyl alcohol according to the method [8-10].

Application of a methanolic solution of heterometallic complex of the General formula Re4-x-WxO4(OMe)12on the media(γ-Al2O3)

1. Determination of moisture content of the carrier in the solvent

As the carrier used γ-Al2O3mainly fraction of 0.5-1.5 mm, the solvent methanol is used.

Calcined at 500°C for 5 hours in a stream of argon sample γ-Al2O3immersed in an excess of methanol and incubated for 2-4 hours in a tightly closed buxe, determine the number pegloticase methanol. Capacity is defined as the ratio pegloticase methanol to the mass media (cm3/g).

2. The deposition of catalyst

The portion of γ-Al2 O3put in a specified number of methanolic solution of heterometallic alloxanic General formula Re4-x-WxO4(OMe)12where x is an integer taking values from 1 to 4, was incubated for 2-4 hours in a tightly closed boxe with constant stirring until complete absorption of the solution by the media.

3. Drying the deposited sample

A carrier coated with a catalyst is dried in two stages: first, carry out the drying in a vacuum Cabinet at a temperature of 150°C for 3-5 hours, and then calcining in a stream of argon at 500°C for 5 hours.

Get the catalyst, which correspond to the data of x-ray phase analysis in figure 1 and figure 2, as well as chemical analysis data (laser spectrometry), presented in table 1.1. and 1.2.:

Table 1.1
Method data laser spectrometry elemental analysis of the sample catalyst composition: 1.3Re-3.7W/Al2O3
% nuclear% mass
W0,39503,7591
Re 0,13221,1934

Table 1.2.
These laser spectrometry elemental analysis of a sample of the catalyst of structure 1,4Re/Al2O3
% nuclear% mass
Re0,15471,3038

Getting alkanovykh and olefinic hydrocarbons

Examples 1-3

Synthesis of alkane-olefin fraction is carried out in a flow reactor with a fixed bed of catalyst, which is used as a pre-restored directly into the reactor at 450°C for 10 hours of γ-aluminum oxide and deposited on the surface of nano-sized solid solution of oxides of Re(1.3%) and W(3,4%). Applied industrial fraction of 2.5-3.0 mm γ-alumina. The heat treatment is carried out using a toroidal electric furnace, which is located outside the tubular reactor. The height of the toroidal furnace corresponds to the height of the reactor.

Upon completion of the heat treatment of the catalyst the temperature of the reactor was lowered to 300°C (sample No. 1), up to 350°C. (example 2), up to 400°C (sample No. 3), create an argon pressure of 5 MPa and start the up flow of vapor source of ethanol on the catalyst, the amount of which in the reactor is 20 cm3with a speed of 0.6 DM3/h·DM3cat.

For 200 minutes passed through the catalyst of 31.6 g of ethanol. During this time, the cooled receivers (1st on the go has a temperature of 0°C, 2 - 15°C) collecting the liquid product.

Gas produced during the reaction, when the process is complete, select in the gas tank and determine the composition of gaseous hydrocarbons With1-With4by gas chromatography. The composition of the liquid products is determined by gas chromatography-mass spectroscopy.

Results on the effect of temperature on the conversion of ethanol in examples 1-3 are presented in table No. 2.

Table No. 2
123
Catalyst1,3Re-1,3 Re-1,3Re-
3,4W/Al2O33,4W/Al2O33,4W/Al2O3
Temperature, °C300350400
Conversion, %729097
Gaseous8,313,222,7
food products rich With1-C4
C10,10,10,4
C25,18,714,3
C43,14,48,0
Gaseousof 21.938,444,5
the unsaturated products2-C4
C212,420,226,8
With30,20,8 0,6
C49,317,417,1
Liquid products:
Alkanes0,91,450,4
C50,40,70,2
C60,50,750,2
Olefins6,57,310,3
C65,56,13,3
C81,01,20,7
Oxygen45,122,27

The products of the conversion of alcohols consist of hydrocarbons, oxygenates and water.

From table 2 it is seen that at temperatures below 350°C is significantly increased you the od of oxygen-containing compounds, while improving the yield of the target alkane-olefin fraction is not observed as compared with example 2. At higher temperatures, as follows from example No. 3, increasing the rate of reactions of cracking, which leads to an increase of the gaseous products, mainly With2.

Example 4-5

The preliminary preparation of the catalyst is carried out analogously to examples 1-3. Upon completion of the heat treatment of the catalyst, the reactor temperature is reduced to 350°C, create an argon pressure of 5 MPa and start the flow of vapor source mixture: example 4 - 80% ethanol and 20% propanol, example 5 - 80% ethanol and 20% butanol on the catalyst, the amount of which in the reactor is 20 cm3with a speed of 0.6 DM3/h·DM3cat.

Next, the synthesis alkane-olefin fraction, the composition of the produced gaseous hydrocarbons With1-With4and liquid products is carried out, as described above.

The results of the conversion of ethanol-propanol and ethanol-butanol in examples 4-5 are presented in table No. 3.

Table No. 3
45
Catalyst1,3Re-3,4W/Al2O3 1,3Re-3,4W/Al2O3
The initial mixture80% ethanol + 20%propanol80% ethanol + 20% butanol
Temperature, °C350350
Conversion, %9492
Gaseous products saturated With1-With429,618
C12,00,1
C2the 13.49,8
C414,28
Gaseous products of unsaturated With2-With423,646
C217,118,5
With30,80,9
C41426,6
Liquid is roducti:
Alkanes10,70,5
C510,70,5
Olefins13,715,2
C540,7
C66,711,5
C72,3-
C80,73
Oxygen9,210,3

The products of the conversion of alcohols consist of hydrocarbons, oxygenates and water.

Example 5 shows that when present in the original mixture of alcohols with an even number of carbon atoms in the carbon skeleton (ethanol and butanol) among the products of transformation is also dominated by hydrocarbons with an even number of carbon atoms. If the initial mixture of the alcohol with an odd number of carbon atoms in the carbon skeleton is observed, as can be seen, and the example 4, the formation of products with even and odd number of carbon atoms in the hydrocarbon skeleton.

Example 6-7

The preliminary preparation of the catalyst is carried out analogously to examples 1-3. Upon completion of the heat treatment of the catalyst, the reactor temperature is reduced to 350°C, create an argon pressure of 5 MPa and begin feeding ethanol vapor on the catalyst content on the surface of nanosized oxide Re(1,3%) (sample No. 6) and oxide W(3,4%) (example No. 7).

Next, the synthesis alkane-olefin fraction, the composition of the obtained gaseous hydrocarbon, C1-C4and liquid products carried out as described above.

In table No. 4 presents the results of the conversion of ethanol depending on the composition of the active components of the catalysts.

Table No. 4
67
Catalyst1,3Re/Al2O33,4W/Al2O3
Temperature, °C350350
Conversion, %4295
Gaseous products saturated With1-C43,27,2
Gaseous products nenasyschennye2-C41,659,7
Liquid products:
Saturated hydrocarbons With5-C8-0,3
Unsaturated hydrocarbon, C5-C8-8,4
Oxygen35,816,7

The products of the conversion of alcohols consist of hydrocarbons, oxygenates and water.

From the results of the above examples, a rhenium does not show catalytic activity, and a tungsten catalyst is noticeably worse combined tungsten-rhenium, which is reflected in the increase of the gas, reducing the yield of the target fraction, as well as the rapid deactivation of the catalyst.

Example 8-9

The preliminary preparation of the catalyst is carried out analogously to examples 1-3. Upon completion of the heat treatment of the catalyst temperature reacto the lower to 350°C, create an argon pressure of 5 MPa and start the flow of vapor source mixture consisting of 70% ethanol and 30% propanol, the catalyst composition Re(1.3%) and W(6,7%).

Next, the synthesis alkane-olefin fraction, the composition of the produced gaseous hydrocarbons With1-C4and liquid products is carried out, as described above.

Table 5 presents the results of the transformation of an alcohol mixture consisting of 70% ethanol and 30% propanol depending on the process temperature.

Table No. 5
89
Catalyst1,3Re-6,7W/Al2O31,3Re-6,7W/Al2O3
Temperature, °C300350
Conversion, %8397
Gaseous9,621
food products rich With1-C4
Gaseous 5,348
products
nenasyschennye2-C4
Liquid products:
Saturated0,71,2
hydrocarbons With5-C8
Unsaturated7,721
hydrocarbons, C5-C8
Oxygen48,37,8

Example 8-9 follows that the tendency to increase the output of oxygen-containing compounds at low temperature is maintained, the increase in the share of the active component of tungsten from 3.4 to 6.7% does not increase the yield of the target fraction5-C8of hydrocarbons.

The results show that in the presence of a catalyst containing only tungsten, significantly increases the gas, the catalyst loses Stabi is inost after 5-6 hours of work; and in the presence of a catalyst containing only the oxide of rhenium, significantly increasing the content of oxygen-containing components, also there is a significant, more than twice the decrease in the conversion of the original spirits.

The temperature dependence of the process detects a narrow range of optimal temperatures 320-370°C, above which there is a sharp increase in gas formation, and below the increase in the output of oxygen-containing components and reducing the conversion of initial reagents.

From the above examples it can be assumed that the kinetic parameters of the reaction is close to many related reactions, thus we have found an interval conditions, providing maximum performance for alkane-olefin fraction.

Thus, the proposed method differs from prototype high stability of the catalyst, allowing the conversion of the original alcohols, equal 85-95%, to increase the output of the olefin-alanovoy fraction5-C8up to 45% and reduce gaseous products1-C2up to 30-35%.

Sources of information

1. J.M.Colluci // Refining magazine September/October 2004.

2. Tretyakov V.F. bordana so-CALLED. // Russian chemical journal, 2003. So XLVII No. 6. p.48.

3. Setterfield Hours Practical course of heterogeneous catalysis. M.: Mir, 1984.

4. RF patent № 2220940 "the Way the floor is placed isoalkanes 8or10".

5. RF patent № 2220941 "Method of obtaining a mixture of isoalkanes4-C16(options)".

6. "Chemical reagents and processes of low-tonnage chemistry / Issue 3, Moscow, Izd-vo'toole. state PED. University n.a. Leo Tolstoy, 2000.

7. Pasahow, Davtovot, Oaanoua, Snejniy, Avernish "Properties and application registergui alcockspruit", XVII Mendeleev Congress on General and applied chemistry. Proc. Reports: Achievements and prospects of chemical science. 2003, Kazan 21-26 September, s.

8. Pasahow, Davtovot "Alcockspruit rhenium" / news of the Academy of Sciences. A series of chemical, 2005, No. 10.

9. Pasahow, Davtovot, Yevzerov, Assalamo "Allocatememory oxide and metallic materials based on rhenium and molybdenum".

10. A.L.Kustov, V.G.Kessler, B.V.Romanovsky, G.A.Seisenbaeva, D.V.Drobot, P.A.Shcheglov ((Supported Re and Mo oxides prepared using binuclear precursors: synthesis and characterization)) / Journal of Molecular Catalysis A: Chemical 216 (2004) 101-106.

1. The catalyst receiving alkane-olefinic hydrocarbons based on γ-alumina, characterized in that it contains an oxide of tungsten and an oxide of rhenium in the following ratio, wt.%:

tungsten1,2-6,7
the rhenium oxide0-1,3
γ-hydroxy) - Rev. aluminum rest

2. The method of obtaining alkane-olefinic hydrocarbons with an even or joint adjacent odd and even numbers of carbon atoms by reaction cross-condensation of ethanol or mixtures thereof with aliphatic alcohols in the presence of a catalyst according to claim 1.

3. The method according to claim 2, characterized in that the reaction cross-condensation is carried out at a temperature of 320-380°C, the inert gas pressure of 1-5 MPa at a feed rate of the mixture of aliphatic alcohols on the catalyst mainly 0,6 DM3/h·DM3cat.

4. The method according to claim 2, characterized in that as the aliphatic alcohols used or butanol, or propanol, or ISO-amyl alcohol, taken in an amount up to 40 wt.%, with respect to ethanol.

5. The method according to claim 2, characterized in that the catalyst is pre-thermoablative at a temperature of 450°C in a stream of hydrogen for 10 hours



 

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4 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: method of obtaining synthetic liquid hydrocarbons from hydrocarbon gases involves catalytic vapour-carbon dioxide conversion of the starting material and recycled products with supply of high-grade heat and obtaining synthetic gas, catalytic processing of the synthetic gas using a Fischer-Tropsch method while tapping low-grade heat through evaporation cooling, division of products obtained from processing synthetic gas into three streams: a mixture of liquid hydrocarbons, water and exhaust gases, and subsequent division of the obtained mixture of liquid hydrocarbons into a fraction of commercial grade hydrocarbons (petrol, kerosene, diesel fuel) and C21+ hydrocarbons, distinguished by that starting gaseous material fed at constant pressure of 0.8-3.0 MPa after purification from sulphur compounds is divided into two streams, one of which together with a portion of waste gases from the Fischer-Tropsch synthesis reactor, carbon dioxide, extracted from exhaust flue gases, and water vapour, are fed into a radial-spiral catalytic reactor for vapour-carbon dioxide conversion, which is carried out at temperature 950-1050°C; the obtained synthetic gas is fed into a steam boiler as heating medium, after partial cooling in which the synthetic gas is further cooled to 20-40°C by an external coolant for moisture removal and is separated from moisture in a surface cooler - drier for synthetic gas, after which it is fed into a Fischer-Tropsch synthesis reactor, and the second stream of starting gaseous material is mixed with another portion of exhaust gases from the Fischer-Tropsch synthesis reactor and fed into the burner of the catalytic reactor as fuel, where before feeding into the burner, the said mixture and air necessary for combustion are heated in a heat recovery unit through partial cooling of flue gases coming out of the catalytic reactor, after which the flue gases are further cooled by an external coolant for moisture removal in the surface cooler-drier for flue gases, further carbon dioxide is removed from the flue gases and fed into the catalytic reactor for vapour-carbon dioxide conversion, flue gases cooled and purified from carbon dioxide are removed from the installation, and the condensate extracted in cooler-driers for synthetic gas and flue gases, and water obtained after separation of Fischer-Tropsch reaction products are purified in a water treatment unit and taken for steam generation, necessary for vapour-carbon dioxide conversion of the starting gaseous material, into a boiler in which the condensate is heated and evaporated using heat of the synthetic gas.

EFFECT: use of said method enable efficient realisation of the proposed method.

4 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of processing products of fermentation of plant biomass to alkane hydrocarbons of the C4-C10 fraction through cross-condensation in the presence of a Fe2O3-MgO/Al2O3 and a Pt/Al2O3 catalyst in ratio Fe:Mg:Pt=13:2:1, at temperature 320-370°C, argon pressure 1-5 MPa and specific feed rate of starting material onto the catalyst equal to 0.4-0.8 dm3/h·dm3 catalyst.

EFFECT: use of the method reduces gas formation and increases output of saturated hydrocarbons.

1 cl, 9 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to versions of an alkylation method, one of which involves: a) alkylation of an alkylation substrate in form of paraffin hydrocarbons with 4-6 carbon atoms using an alkylating agent in form of olefins with 2-6 carbon atoms, with formation of an alkylate in the reactor; b) extraction of an exhaust stream from the reactor, containing alkylate and alkylation substrate; c) flash evaporation of at least part of the exhaust stream of the reactor with formation of supply for a heat exchanger with coolant, containing alkylate and alkylation substrate, where the supply for the heat exchanger with coolant has the same composition as at least part of the exhaust stream of the reactor; d) heating at least part of the supply for the heat exchanger with coolant in the said heat exchanger and extraction from the heat exchanger with coolant of an exhaust stream formed by the supply for the heat exchanger, which contains alkylate and alkylation substrate; e) passing at least part of the exhaust stream from the heat exchanger to a separator for separating liquid phase of the exhaust stream from vapour and extraction from the separator of a vapour phase which contains alkylation substrate, and a liquid phase which contains alkylate; f) compressing the vapour phase with formation of a compressed stream which contains alkylation substrate; g) at least partial condensation of at least part of the compressed stream with formation of a condensed stream which contains alkylation substrate; h) indirect heat exchange in the heat exchanger with coolant from at least part of the condensed stream to at least part of the supply for the heat exchanger with coolant, with formation of a cooled return flow which contains alkylation substrate; i) returning at least part of the cooled return flow into the reactor, and j) extraction of alkylate from the liquid phase.

EFFECT: returning light components such as hydrogen chloride and prevention of loss of hydrogen chloride without excess expenditure on compression.

12 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of aromatising alkanes and involves bringing alkanes, which contain from one to four carbon atoms, into contact with a Pt/ZSM-5 catalyst which is deposited on MFI zeolite, the lattice of which consists of aluminium, silicon and oxygen. Use of the given catalyst during aromatisation of alkanes prevents formation of methane and increases BTX selectivity.

EFFECT: higher content of ethane than methane in the light gas fraction enables use of exhaust gas as raw material for cracking apparatus.

15 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a mixture of C4-C16 isoalkanes by bringing aliphatic alcohol - ethanol, 2-methyl-1-propanol, 3-methyl-1-butanol in an inert gas medium at 300-420°C, pressure 30-80 atm, bulk speed 0.2-0.8 h-1, into contact with a catalyst composition, which contains a hydride phase of an iron-titanium intermetallic compound, modified with group IV-VII metals, aluminium-platinum catalyst and a transition metal oxide, characterised by that, the transition metal oxide used is magnesium oxide in mass ratio 10:1:(0.8-1.2).

EFFECT: catalyst used in the method is highly active for a long period of time and the given method also widens the raw material base of aliphatic alcohols used.

1 cl, 7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a benzene hydrogenation and ring opening method and isomerisation of C5-C6 paraffins of starting paraffin material, which contains normal paraffins C5-C6 and at least 1 wt % benzene, involving: (a) feeding starting material, without tapping or condensing hydrogen, into a drier for removing water and obtaining dried starting material containing not less than 0.5 wt % water; (b) combination of dried starting material with a hydrogen-rich gas stream with formation of a mixed load; (c) feeding the mixed load at temperature ranging from 38 to 232°C into the hydrogenation zone, and bringing the said mixed load into contact with a hydrogenation catalyst under hydrogenation conditions in order to saturate benzene and form a stream of products, removed from the hydrogenation zone, with temperature ranging from 149 to 288°C and containing less than 1.5 wt % benzene; hydrogenation conditions include excess pressure from 1400 kPa to 4800 kPa, hourly space velocity for feeding the load from 1 to 40 h-1 and ratio of contained hydrogen to hydrocarbons ranging from 0.1 to 2; (d) regulation of temperature of the stream of product removed from the hydrogenation zone in the interval from 104 to 204°C through at least heat exchange of the product removed from the hydrogenation zone with the mixed load; (e) feeding at least part of the product removed from the hydrogenation zone into the isomerisation zone and bringing the stream of the said load into contact with an isomerisation catalyst under isomerisation and ring opening conditions at excess pressure ranging from 1380 to 4830 kPa; and (f) extraction of the isomerisation product obtained in the isomerisation zone. The invention also relates to a device for realising the proposed method.

EFFECT: use of the proposed invention provides for economisation by reducing the number of units of the equipment used and equipment expenses, and also reduces amount of hydrogen required for carrying the process.

9 cl, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of isomerising normal butane containing initial material, containing at least 50 wt % normal butane to an isomerate which contains isobutane, involving: (a) isomerisation of the initial material under isomerisation conditions, involving presence of isomerisation catalyst, until an output isomerisation stream is obtained, containing normal butane, but with less concentration than in the initial isomerisation material; (b) distillation of at least part of the output isomerisation stream until a low-boiling fraction is obtained, containing isobutane and light paraffins, where at least 80 wt % of the low-boiling fraction is isobutane, and a high-boiling fraction, containing normal butane and at least 10 wt % isobutane; (c) bringing at least part of the fraction containing normal butane from stage (b) into contact with medium at the retentate side of a permeation-selective membrane, with efficiency index of flow of C4 permeate equal to at least 0.01 and pressure difference between media on both sides of the membrane, which allows for obtaining a retentate fraction containing at least 80 wt % isobutane, and for obtaining a permeate fraction at the permeate side, after passage through the membrane, with high concentration of normal butane; and (d) tapping off retentate fraction from stage (c).

EFFECT: simplification of method.

10 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention refers to the method of purification of paraffin hydrocarbons from methanol admixtures. The said purification is carried out in the presence of hydrogen on the catalyst containing one of the metal selected from Ni and Pd applied on the inert carrier at temperature 30-100°C, mole excess hydrogen : methanol in the range (5-50): 1 and volume hydrocarbons feed rate 1-6 hrs.-1.

EFFECT: simplifying and cheapening of the process.

1 cl, 9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to method of polymerisation of raw material flow containing C5-C6 hydrocarbons, which includes: loading of hydrogen and raw material, containing at least, normal C5-C6 hydrocarbons into isomerisation zone and contacting of hydrogen and raw material with isomerisation catalyst in conditions that favour increase of degree of hydrocarbons branching in raw material flow and ensuring formation of outgoing flow from isomerisation zone, which contains, at least, butane, normal pentane, normal hexane, methylbutane, dimethylbutane, methylpentanes and hydrocarbons which have seven or more carbon atoms, isomerisation conditions including temperature from 40° to 235°C and pressure 70 kPa abs. to 7000 kPa abs; passing outgoing flow from isomerisation zone through deisohexanizer zone in order to divide it into four flows, flow outgoing from upper part of deisohexaniser zone, containing, at least, butane, first side flow from deisohexaniser zone, containing, at least, methylbutane and dimethylbutanes, second side flow from deisohexaniser zone, containing, at least, methylpentanes and normal hexane, and lower flow from deisohexaniser zone, containing, at least, hydrocarbons, consisting of seven and more carbon atoms; and supply of first side flow from deisohexaniser zone into zone of isomerizate stripping in order to separate upper flow from isomerisate desorber which contains, at least, butane, from product flow from zone of isomerisate stripping, containing methylbutane and dimethylbutanes.

EFFECT: application of claimed method allows to reduce capital outlays and reduce cost of energy supply due to excluding of column-stabiliser.

9 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to two versions of a method of converting a stream of material which contains oxygenate with 1-10 carbon atoms, in the reaction zone of a fluidised layer. One of the versions involves conversion in the zone of a fluidised layer, which includes a reactor with a circulating fluidised catalyst layer in conversion conditions in the presence of a catalyst for obtaining a stream of a product which contains light olefins, in which one or more inner surfaces of the reaction zone has a protective layer which is more resistant to metal-catalysed coking than a steel alloyed surface, where the protective layer contains one or more elements from a group comprising tin, chromium, antimony, aluminium, germanium and silicon.

EFFECT: use of the present method solves the problem of protecting surfaces of the reaction zone from metal-catalysed coking.

7 cl, 3 ex, 4 dwg

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