The method of obtaining aliphatic alcohols for the production of motor fuels

 

(57) Abstract:

Use: in the production of motor fuels. The essence of the invention: aliphatic alcohols obtained from the synthesis gas in the presence of atlantabased gas concentration in the gas phase is 0.05 to 3.0 vol.%, better 0,25 - 3,00% vol., when the ratio of H2/CO in the synthesis gas 1,8 - 2,2, Zn-Cr-K-V-catalyst 378 - 400C. for 1 h.p. f-crystals, 1 table.

The invention relates to the chemical, petrochemical and chemical industry and can be used in joint receipt of methanol and aliphatic alcohols WITH2-C4for their application as high-octane components of motor fuels. A known method for simultaneous production of methanol and aliphatic alcohols WITH2-C4+...from synthesis gas installation flow type with the organization of the circulation gas [1]

Closest to the claimed solution is the way [2] joint production of methanol and aliphatic alcohols WITH2-C4+...from synthesis gas at elevated temperature and pressure by hydrogenation of carbon oxides in the presence of a solid oxide catalyst (prototype).

The disadvantage of this method [2] is a significant predominance of methanol in peoplewe adding thereto synthesized by the method [2] alcohols to increase the octane number instead of the highly toxic Tetra-ethyl lead. Thus, when a mixture of alcohols (15 wt.) with a ratio of1:C4+...-5,2 with gasoline (85) fuel stratified already at a temperature of minus 5aboutWith, and with the addition of aliphatic alcohols WITH1-C4+...with a ratio of1: C4+...is 12.5 and the same conditions fuel stratified even when the temperature plus 15aboutC. the disadvantage of the prototype [2] is also a low concentration of aliphatic alcohols with the number of carbon atoms 5 and above, which reduces the caloric content of the composite fuel.

The aim of the invention is to increase the selectivity of the process for aliphatic alcohols with the number of carbon atoms 4 and above, as well as increasing the concentration of alcohols WITH5+...in the resulting reaction mixture.

This objective is achieved in that during production of alcohols from synthesis gas on a zinc-chromium-potassium-vanadium catalyst at elevated temperatures and pressures, according to the invention, in the area of catalysis, together with the synthesis gas is introduced atlantagay gas. Concentration atlantabased gas mixed with the synthesis gas is in the range of 0.05-3,00 about. mainly 0,25-3,00 about. The ratio of N2/CO in the synthesis gas is 1.8-2.2 and the process is conducted at 378-400aboutC.

2/FROM 1.8 to 2.2, the concentration of CO20,8 about. inert components methane+nitrogen not more than about 4. served in the area of catalysis reactor flow type. The catalyst for the synthesis of modified zinc-chromium-potassium-vanadium.

The composition of the catalyst, wt. zinc oxide 64,7; chromium oxide 28,8; the oxide of potassium 2,5; vanadium pentoxide 1,0; graphite 3,0, including impurities, not more than wt. mass fraction of iron in terms of Fe2O30,04; mass fraction of total sulphur in terms of SO3the 0.01 mass fraction of the sum of alkali metals in terms of K2About 0,04. The size of the granules of catalyst 2x3 mm; the rich density of 1.65 g/cm3the volume of catalyst in the reactor 40 cm3; mass of catalyst 66, the Temperature at the entrance to the area of catalysis 378aboutWith output 400aboutC. the Pressure of the synthesis 24,9 MPa. In the area of catalysis serves synthesis gas at a rate of 600 nl/h together with atlantabased gas. Atlantagay gas is produced by conversion of methanol and/or ethanol and/or propanol and/or butyl alcohols vysokoglinozemistykh zeolite catalysts or in the process of discharge from the coke oven gas, or as a gaseous waste products of high-pressure polyethylene.

The composition atelinae,8; H22,7. Concentration atlantabased gas (ESG) in the synthesis gas about 0. Performance 1 cm3catalyst for aliphatic alcohols WITH1-C4+...-0,73 g/h Ratio1: C4+...in the mixture of alcohols -4,72. The concentration of aliphatic alcohols WITH4+...the products of synthesis is 16,71 wt. including alcohols WITH5+...-2,71 wt. (see table).

P R I m m e R 2. Conditions for the synthesis of aliphatic alcohols are the same as in example 1. Concentration atlantabased gas (ESG) in the synthesis gas is 0.05. Data on the performance of the catalyst for aliphatic alcohols and their composition is presented in table. The value OF1: C4+...- -4,41. The concentration of aliphatic alcohols WITH4+...the products of synthesis is 17,63 wt. including alcohols WITH5+...- -2,96 wt.

P R I m e R 3. Conditions for the synthesis of aliphatic alcohols are the same as in example 1. Concentration atlantabased gas (ash) mixed with the synthesis gas 0,25 about. Data on the performance of the catalyst and the composition of the aliphatic alcohols is given in the table. The value OF1: C4-...to 3.58.

The concentration of alcohols WITH4+...is 20,72 wt. including alcohols WITH5+...4,29 wt.

P R I m e R 5. Conditions for the synthesis of aliphatic alcohols are the same as in example 1. Concentration ash about 1. Data on the performance of the catalyst and the composition of the aliphatic alcohols is presented in the table. The ratio of alcohols WITH1: C4+...2,44, the concentration of alcohols WITH4+...-26,82 wt. including5+...-6,82 wt.

P R I m e R 6. Conditions for the synthesis of aliphatic alcohols are the same as in example 1. Concentration ash about 2. Data on the performance of the catalyst and the composition of the alcohols listed in table. The ratio of alcohols WITH1:C4-2,28, the concentration of alcohols WITH4+...-2828 wt. including5+...7 wt.

P R I m e R 7. Conditions for the synthesis of aliphatic alcohols are the same. Concentration ash in the synthesis gas 3 about. Data on the performance of the catalyst and the composition of the alcohols shown in table. The ratio of alcohols WITH1: C4...2,68, the concentration of alcohols WITH4+...25,17 wt. including5+...of 6.4 wt.

P R I m e R 8. The process is conducted similarly to examples 1-7, eljnosti catalyst and the composition of the alcohols listed in table. The ratio of alcohols WITH1: C4+...4,6, the concentration of alcohols WITH4+...-17,09 wt. including5+...-of 2.83 wt.

Adding alcohols (15%) obtained by the proposed method (example 1-8), to the base fuel (85%) octane 68-70, the octane number of the fuel composition is increased up to 76-78.

While motor fuel prepared with addition of alcohols synthesized according to example 1 of the method, stratified at -16aboutWith, and the fuel is prepared with the addition of alcohols synthesized according to example 8 splits at -18aboutWith that does not meet the requirements of THE 38.101909-82 on buntmetall mixture containing 15 wt. alcohols (BMS-15).

Alcohols synthesized according to examples 2, 3, 4, 5, 6, 7 cause delamination at -20, -35, -38, -40, -45 and -39aboutWith, respectively, which satisfies the requirements of THE 38.101909-82 BMS-15 to measure the turbidity. The cloud point was determined according to GOST 5066-56. Thus, to improve knock resistance of motor fuel and ensure its stability against separation composition of aliphatic alcohols should be selected so that the ratio of C1: C4+...it did not exceed a 4.4. Such a composition anego 0.05 to about 3. in Gaza. Moreover, the greatest stability in a mixture with gasoline have the alcohols obtained when the concentration of ash in the synthesis gas 0.25 to about 3.

The use of the proposed method of implementation of the process will allow you to get aliphatic alcohols desired composition. By mixing them with gasoline (hydrocarbons) is quite stable fuel composition even at low temperatures, which, in combination, can reduce the consumption of motor fuels by bringing in resources motor fuels non-oil raw materials origin (natural gas, coke oven gas, and other). When using alcohol significantly increases the quality of motor fuels due to the high octane number of aliphatic alcohols WITH1-C4+...[1, p 217] while reducing costs in the process of refining in vysokoavtomatizirovannyh hydrocarbon fractions. Increases the output of motor fuels, completely stopped the use of highly toxic lead compounds polluting the environment.

1. The METHOD of OBTAINING ALIPHATIC ALCOHOLS FOR the PRODUCTION of MOTOR FUELS from synthesis gas at elevated temperature to the zinc-chromium-potassium-vanadium catalyst, characterized in that in the area of catalysis venea H2/CO in the synthesis gas is 1.8 to 2.2, and the process is conducted at 378 400oC.

2. The method according to p. 1, wherein the process is conducted when the content atlantabased gas in a gas mixture is equal to 0,25 3,00 about.

 

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1 tbl, 11 ex, 1 dwg

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1 tbl, 2 dwg

FIELD: chemistry.

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4 cl, 3 tbl, 3 dwg, 2 ex

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2 cl, 1 tbl, 8 ex

FIELD: method for production of alcohol-containing solvents based on waste from ethanol production from food-grade raw materials.

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3 cl, 1 dwg, 3 ex, 3 tbl

FIELD: organic chemistry, fuel production.

SUBSTANCE: claimed method includes feeding of heated hydrocarbon-containing and oxygen-containing gas in reaction unit, vapor phase oxidation of hydrocarbon-containing gas at 250-450°C and pressure of 2.0-10 MPa under near isothermal conditions; cooling of reaction mixture in heat exchangers, separation of gas and liquid phases of reaction mixture. separation of obtained methanol solution of formaldehyde, C2-C4-alcohols and methanol, methanol and gas phase after separation into reactors; catalytic methanol conversion on zeolite catalyst at 350-450°C and pressure of 3-8 MPa; cooling of produced reaction mixture in heat exchangers; separation of gas and liquid phases of reaction mixture; separation of aqueous fraction and synthetic diesel fuel liquid fractions, including fraction of liquid hydrocarbons, corresponding to motor gasoline having octane number of at least 92.

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5 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of producing aliphatic alcohols. The method involves feeding the first hydrocarbon stream, obtained using the Fischer-Tropsch method, containing olefins and paraffins. The Fischer-Tropsch stream contains 5-80% olefins, with 10-17 average number of carbon atoms. This hydrocarbon stream is fed into the hydrogenation-isomerisation installation, where there is dehydrogenation of at least part of paraffins in the Fischer-Tropsch hydrocarbon stream to olefins. The installation is also made such that, there is isomerisation of at least part of linear olefins to branched olefins, in the presence of a dehydrogenation-isomerisation catalyst, containing zeolite in hydrogen form, with a ferrierite isotope structure. Duration of stay is such that, conversion of paraffins to olefins is lower than 40%, and at least part of unreacted components of the hydrocarbon stream, obtained using the Fischer-Tropsch method and at least, part of products of the dehydration and isomerisation reaction form a second hydrocarbon stream. This second hydrocarbon stream contains olefins and paraffins. At least some of the olefins in the second hydrocarbon stream are branched. The method also involves feeding at least part of the second hydrocarbon stream into a hydroformylation installation. The hydroformylation installation is made such that, at least part of the olefins in the second hydrocarbon stream can be undergo hydroformylation, obtaining aliphatic alcohols with average number of carbon atoms from 11 to 18, and at least part of the obtained aliphatic alcohols contain branched alkyl groups.

EFFECT: invention can be used for producing surface active substances, detergents and sulphates.

9 cl, 7 tbl, 6 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: method includes introduction of hydrocarbon Fisher-Tropsch flow, containing olefins and paraffins, said hydrocarbon Fisher-Tropsch flow containing from 5 to 80% of olefins, which have average number of carbon atoms from 10 to 17, and paraffins, into installation of hydration, where hydration installation is made in such way as to hydrate at least part of olefins in hydrocarbon Fisher-Tropsch flow to paraffins, and where at least part of components of hydrocarbon Fisher-Tropsch flow, which did not react, and at least part of hydrated olefins form second hydrocarbon flow; introduction of second hydrocarbon flow into installation of dehydration-isomerisation, where installation of dehydration-isomerisation is made in such way as to hydrate at least part of paraffins in second hydrocarbon flow to olefins, and where installation of dehydration-isomerisation is also made in such way as to isomerize at least part of linear olefins to branched olefins in presence of dehydration-isomerization catalyst, which contains hydrogen form of zeolite, having isotopic lattice structure of ferrierite, and where period duration is such that transformation of paraffins into olefins is lower than 40% mol, and where at least part of second hydrocarbon flow components that did not react, and at least part of products of dehydration and isomerisation reactions form third hydrocarbon flow, and third hydrocarbon flow contains olefins and paraffins, and where at least part of olefins in third hydrocarbon flow represent branched olefins; and introduction of at least part of third hydrocarbon flow into installation of hydroformilation, where installation of hydroformilation is made in such way as to hydroformilate at least part of olefins in third hydrocarbon flow obtaining aliphatic alcohols with average number of carbon atoms from 11 to 18, and where at least part of obtained aliphatic alcohols contain branched alkyl group.

EFFECT: reduction of expenditure.

18 cl, 7 tbl, 5 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: proposed method of producing branched olefins involves dehydrogenation of an isoparaffin composition, containing 0.5% or less quaternary aliphatic carbon atoms, on a suitable catalyst. The above mentioned isoparaffin composition contains paraffins with 7 to 35 carbon atoms. These paraffins, or at least part of their molecules, are branched. The average number of branches per paraffin molecule ranges from 0.7 to 2.5, and the branches include methyl and, optionally, ethyl branches. The above mentioned isoparaffin composition is obtained through hydroisomerisation of paraffin, and the above mentioned branched olefins contain 0.5% quaternary carbon atoms or less. The paraffins are produced using Fischer-Tropsch method. The invention also relates to the method of producing a surface active substance from olefins, obtained using the method described above.

EFFECT: improvement of operational characteristics.

5 cl, 4 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method includes introduction of first hydrocarbon flow, including olefins and paraffins, which have number of carbon atoms from 4 to 30, into installation of isomerisation, where installation of isomerisation is intended for isomerisation of at least part of linear olefins in first hydrocarbon flow into branched olefins, and where at least part of components of first hydrocarbon flow, that have not reacted, and at least part of obtained branched olefins form second hydrocarbon flow; introduction of at least part of second hydrocarbon flow into installation of hydroformylation, where installation of hydroformylation is intended for hyroformylation of at least part of olefins in second hydrocarbon flow with formation of aliphatic alcohols and where at least part of obtained aliphatic alcohols include branched alkyl group and where at least part of components of second hydrocarbon flow that have not reacted, and at least part of obtained aliphatic alcohols form flow of hydroformilation reaction; separation of at least part of hydroformylation reaction flow in order to obtain flow of product, containing aliphatic alcohols, and flow of paraffins and olefins that have not reacted, and introduction of at lest part of flow of paraffins and olefins that have not reacted into installation of dehydration, where installation of dehydration is intended for dehydration of at least part of paraffins in flow of paraffins and olefins that have not reacted for obtaining olefins and where at least part of obtained olefins leave installation of dehydration forming olefin hydrocarbon flow and introduction of at least part of olefin hydrocarbon flow into installation of isomerisation.

EFFECT: obtained aliphatic alcohols can be used for obtaining surface-active substances, sulphates.

21 cl, 6 tbl, 3 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a gas-phase method of catalytic conversion of lower alkanes. A method is described for catalytic conversion of lower alkane, containing up to 5 carbon atoms, into at least one product which is chosen from a group consisting of alcohols, aldehydes and their mixture, involving bringing said lower alkane into contact with an oxidising agent in the presence of a catalyst, containing a platinum complex which is deposited on a carrier, with the following structure: in which: L is a ligand, which is chosen from amino-ligands, hydroxyl ligands and imidazolyl ligands; A is a ligand which is chosen from hydroxyl ligands, chloro-ligands and amino-ligands; M is a metal cation in the catalyst carrier, which is chosen from cations of aluminium, silicon, zirconium, titanium and molybdenum; and n is an integer, which is chosen from 4, 2 and 1, Pt in the catalyst is a cation in a valent state which is chosen from valent states (IV), (II) and (I), which correspond to numerical values of n, where the said platinum cation forms the central core of the platinum complex, ligands L and ligands A surround the central core and ligands L chemically bond the complex to the surface of the carrier, under which metal cations M are localised.

EFFECT: high conversion and selectivity of formation of methanol in direct oxidation of methane or natural gas with air or molecular oxygen in the presence of catalyst promoters.

15 cl; 4 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: alcohol-containing mixture is mixed with acetic or propionic aldehyde in weight ratio 100:(10-45). The obtained mixture is held in the presence of an acid catalyst until stratification and the organic layer is separated from the aqueous layer. The organic layer undergoes deep dehydration by heating to boiling point with reclamation of aldehyde via fractionation to obtain anhydrous alcohol or a mixture of alcohols in the still residue. The acid catalyst used is preferably an ion-exchange resin in hydrogen form or a synthetic zeolite.

EFFECT: method is universal since it has high process flexibility with respect to raw material, and provides considerable efficiency when dehydrating an alcohol-containing mixture containing alcohols with three to five carbon atoms with very low power consumption.

5 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of copolymerising olefins, according to which a) a first starting olefin material is prepared, mainly consisting of Cn-olefins, and a second starting olefin material, mainly consisting of Cm-olefins, where n and m independently denote different integers from 2 to 12, and where the second starting olefin material is characterised by degree of branching of olefins defined in form of an ISO index ranging from 0 to 18, and is obtained via dimerisation of raffinate II, mainly consisting of isomeric n-butenes and n-butane, in the presence of a nickel-containing oligomerisation catalyst, and b) the first and second starting olefin materials react on a heterogeneous olefin oligomerisation catalyst based on sheet and/or framework silicates. The invention also relates to codimers obtained using said method, a method of producing alcohols according to which said olefin codimers undergo hydroformylation followed by hydrogenation of mixtures of alcohols obtained using said method.

EFFECT: high efficiency of the method.

18 cl, 2 tbl, 1 ex

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