EA017229B1 - A process for converting a hydrocarbon feedstock with the electrolytic recovery of halogens - Google Patents

A process for converting a hydrocarbon feedstock with the electrolytic recovery of halogens Download PDF

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Publication number
EA017229B1
EA017229B1 EA200970960A EA200970960A EA017229B1 EA 017229 B1 EA017229 B1 EA 017229B1 EA 200970960 A EA200970960 A EA 200970960A EA 200970960 A EA200970960 A EA 200970960A EA 017229 B1 EA017229 B1 EA 017229B1
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Eurasian Patent Office
Prior art keywords
oxygen
hydrogen
gas
hydrocarbons
cathode
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EA200970960A
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Russian (ru)
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EA200970960A1 (en
Inventor
Филип Гроссо
Эрик В. МакФарланд
Джефри Х. Шерман
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Грт, Инк.
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Priority to US93022007P priority Critical
Application filed by Грт, Инк. filed Critical Грт, Инк.
Priority to PCT/US2008/006244 priority patent/WO2008143940A2/en
Publication of EA200970960A1 publication Critical patent/EA200970960A1/en
Publication of EA017229B1 publication Critical patent/EA017229B1/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/24Electrolytic production of inorganic compounds or non-metals of halogens or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • C07C1/30Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/02Alkenes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONAGEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONAGEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other processes not covered before; Features of destructive distillation processes in general
    • C10B57/04Other processes not covered before; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06Other processes not covered before; Features of destructive distillation processes in general using charges of special composition containing additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00Refining of hydrocarbon oils in the absence of hydrogen, with other chemicals
    • C10G29/02Non-metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/02Electrolytic production of inorganic compounds or non-metals of hydrogen or oxygen
    • C25B1/04Electrolytic production of inorganic compounds or non-metals of hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1025Natural gas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30Aromatics
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/013Alloys
    • H01L2924/014Solder alloys
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources
    • Y02E60/366Hydrogen production from non-carbon containing sources by electrolysis of water
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10General improvement of production processes causing greenhouse gases [GHG] emissions
    • Y02P20/14Reagents; Educts; Products
    • Y02P20/141Feedstock
    • Y02P20/145Feedstock the feedstock being materials of biological origin

Abstract

An improved continuous process for converting methane, natural gas, and other hydrocarbon feedstocks into one or more higher hydrocarbons, methanol, amines, or other products comprises continuously cycling through hydrocarbon halogenation, product formation, product separation, and electrolytic regeneration of halogen, optionally using an improved electrolytic cell equipped with an oxygen depolarized cathode.

Description

The invention relates to an improved continuous method of converting methane, natural gas and other hydrocarbons into one or more higher hydrocarbons, methanol, amines or other products, including a continuous cycle of hydrocarbon halogenation stages, product formation, product separation and electrolytic halogen regeneration, optionally using an improved electrolytic cell equipped with a cathode with oxygen depolarization.

017229 Β1

Scope of invention

The present invention relates to a method for converting natural gas and other types of hydrocarbons into more valuable products, such as fuel hydrocarbons, methanol and aromatics.

Background of the invention

Application for US Patent No. 11/703358 (hereinafter referred to as Application 358), entitled The Continuous Method for Converting Natural Gas to Liquid Hydrocarbons, filed on February 5, 2007, based on provisional application for US Patent No. 60/765115 filed on February 3, 2006 , describes a continuous method of reacting molecular halogen with a hydrocarbon feed to produce higher hydrocarbons. In one embodiment, the method includes the steps of halogenation of alkanes, reproportionation of polyhalogenated compounds to increase the amount of monohalides formed, oligomerization (C-C addition) of alkyl halides to form products with a large number of carbon atoms in the molecules, separation of the products from the halogen, and continuous recovery of the halogen and extraction of the molecular halogen of water. Hydrohalic acid (for example, HBr) is separated from liquid hydrocarbons in a liquid separating device and then converted to molecular halogen (for example, bromine) by reaction with an oxygen source in the presence of a catalyst — a metal oxide. Application 358 is fully incorporated into this description by reference.

Application 358 offers a significant improvement in the C-H bond activation process known in the art and industrial methods for converting hydrocarbon feedstocks to more valuable products. The present invention is based on application 358, which proposes the use of electrolysis for the regeneration of molecular halogen (for example, Br 2 , C1 2 ) from hydrohalic acid (for example, HBg, HC1).

Electrolysis of aqueous solutions with evolution of hydrogen and oxygen is a well-known way of producing hydrogen using electrical energy. Similarly, halogens are released by electrolysis of halide solutions or metal halide vapors. The traditional method of industrial hydrogen production is based on the reforming of hydrocarbons with water (water vapor) to produce carbon monoxide and molecular hydrogen:

СН) + Н 2 О -> СО + ЗН 2 ΔΗ = +206 kJ / mol

С Х Н У + хН 2 О - »хСО + (х + у / 2) Н 2 ΔΗ» 0 kJ / mol.

Energetically unfavorable reforming reaction can be compared with the full exothermic oxidation of hydrocarbons in oxygen with the formation of low-energy products - water and carbon dioxide:

СН) + 2О 2 -с ССЬ + 2Н 2 О ΔΗ = -882 kJ / mol

С ' х Г1 у + (х + у / 2) О 2 -> хСО 2 + у / 2Н 2 О ΔΗ

As a rule, the reforming process is carried out in conjunction with complete oxidation to obtain the energy needed to undergo a different endothermic reaction. The resulting total reaction produces carbon oxides, and hydrogen, and can be exploited almost isoenergetically:

С „Н т + хО 2 + уН 2 О -» (п-т) СО + тСОг + (т / 2 + у) Н 2 .

Alternatively, hydrogen can be obtained by dissociating water:

H 2 O - * 1 / 2O 5 + H 2 ΔΗ = 286 kJ / mol H 2 .

Despite the fact that the reaction is energetically unfavorable, it can be carried out by electrolysis using an amount of electricity of 2x10 5 C / g-mol H 2 . Water is a source of both hydrogen and oxygen, and high activation energy when oxygen is generated requires an overvoltage of approximately 1.6 V and a stoichiometric current. In practice, the required electrical energy is approximately 300 kJ / mol H 2 .

Upon receipt of halogen by electrolysis of halide salts, for example in the chlor-alkali process, halogen (C1 2 ) and alkali (ΝαΟΗ) are obtained in an aqueous solution of the salt (nC1) from the halide anion and water. Again the source of hydrogen is water. Similarly, you can get bromine from bromide salts (Ν; · ιγ). In the latter case, the formation of molecular halogen from a halide anion is energetically and kinetically advantageous compared to the formation of oxygen, since it requires less overvoltage (1.1 V compared to 1.6 V):

H, 0 + KaVg - * Br 2 + H 2 + MaOH.

with an amount of electricity of 2x10 5 C / g-mol H 2 and a significant reduction in the amount of electric power required (as compared with pure H 2 O) - up to approximately 200 kJ / g-mol H 2 .

- 1 017229

Many attempts have been made to develop economically viable methods for producing hydrogen. In principle, direct electrochemical oxidation of hydrocarbons with oxygen (as in a solid oxide fuel cell) and / or water is possible with the formation of hydrogen; nevertheless, this path leads, as a rule, to the formation of complex, difficult to separate intermediate products and is not cost-effective. Another way to remove hydrogen from hydrocarbons is to stage a partial oxidation with halogen (preferably bromine). The main advantage is that complete oxidation of hydrocarbon to carbon dioxide cannot occur, and hydrogen passes into less stable HBg (AN of formation = -36 kJ / mol) than water ^ of formation of 286 kJ / mol) .

StsN sh + r / 2Vg g - "SpNifVgr + pHBr

SpNgBc + x / 2Br 2 C „H g Bg p + xHBg.

The final products remaining after the removal of HBg depend on the reaction conditions and can consist of mixtures of coke and brominated and perbrominated hydrocarbons. C x + C y H 1 I Br Br + C g h. Incineration of these end products in an atmosphere of oxygen containing trace amounts of water can be used to generate heat and produce carbon oxides and convert the residual bromine to HBg

Cx - · - C y H 2 Br, + CrBr i + n / 2O 2 + (ί + ς) / 2Η 2 Ο -> (x + y + g = n) CO 2 + (1 + c) HBg.

Another method of producing hydrogen, based on the electrolysis of HBr, according to the available data, allows to save about 25% of energy compared to electrolysis of water. However, in this process, it is necessary to convert the bromine obtained during the electrolysis back into HBr, and this step of converting represents the main disadvantage of the HBr uptake of electrolysis to hydrogen. On the contrary, the present invention uses bromine generated during the electrolysis process to obtain valuable products, rather than simply converting it back to HBg.

Summary of Invention

The present invention combines the thermal (non-electrochemical) ability of halogens (preferably bromine) to react with hydrocarbons to produce hydrogen halide (preferably HBg) and reactive alkyl halides or other carbon-containing intermediates that can be converted to subsequent products more easily than the original hydrocarbon, with simple hydrogen halide electrolysis or halide salts, creating a common process with significantly higher efficiency. The use of halogens prevents the complete oxidation of hydrocarbon to carbon dioxide and allows you to consistently produce partially oxidized products.

In one aspect of the invention, a continuous process for converting a hydrocarbon feedstock to one or more higher hydrocarbons includes.

(a) the formation of alkyl halides by reacting a molecular halogen with a hydrocarbon feedstock under process conditions sufficient to form alkyl halides and hydrogen halide, preferably with almost all molecular halogen consumed;

(b) the formation of higher hydrocarbons and hydrogen halide by contacting the alkyl halides with the first catalyst under process conditions sufficient to form higher hydrocarbons and hydrogen halide;

(c) separating higher hydrocarbons from hydrogen halide;

(ά) electrolytic conversion of hydrogen halide to hydrogen and molecular halogen, whereby this halogen can be reused;

(e) repeating steps from (a) to (ά) the desired number of times.

These steps may be carried out in the order indicated or, alternatively, in a different order. The electrolysis is carried out in aqueous media or in the gas phase. Optionally, the alkyl halides are reproportioned by reacting some or all of the alkyl halides with the feed of alkanes, and the fraction of monohalogenated hydrocarbons present is increased. In addition, in some embodiments, the hydrogen produced in this process is used to generate energy.

In the second aspect of the invention, a continuous process for converting a hydrocarbon feed to methanol comprises.

(a) the formation of alkyl halides by reacting a molecular halogen with a hydrocarbon feedstock under process conditions sufficient to form alkyl halides and hydrogen halide, preferably with almost all molecular halogen consumed;

(b) the formation of methanol and alkali metal halide by contacting the alkyl halides with an aqueous solution of alkali under process conditions sufficient to form methanol and an alkali metal halide;

(c) separating methanol from an alkali metal halide;

(ά) electrolytic conversion of an alkali metal halide into hydrogen or molecular halogen and an aqueous alkali solution, whereby halogen and alkali can be used to repeat

- 2 017229 but;

(e) repeating the steps from (a) to (s) the desired number of times.

These steps may be carried out in the order indicated or, alternatively, in a different order. Optionally, polyhalogenated hydrocarbons are reproportioned by reacting some or all of the alkyl halides with the feed of alkanes, and the fraction of monohalogenated hydrocarbons present is increased.

The production of methanol in this way requires that the reaction of alkyl halides with an aqueous solution of alkali be carried out under alkaline conditions. However, the electrolysis process produces alkali and acid in stoichiometrically equivalent amounts. Thus, simply re-combining all the alkali with all the acid would result in a neutral solution. The method described here provides the disproportionation of the acid and base, so that the alkali is available in more than enough quantities to react with alkyl bromides to achieve alkaline conditions. The acid removed at the disproportionation stage is later re-combined with an excess of alkali after methanol and other products have been obtained and separated.

In some embodiments, it may be necessary to maintain the anolyte under acidic conditions, which may require the addition of a small amount of acid. The separation of part of the acid can be carried out by a liquid-phase process or, alternatively, by means of a regenerable solid reagent or an adsorbent. In addition, it is possible to inject an acid from an external source, generated either locally or remotely. Alternatively, total excess acid can be achieved by removing a small amount of alkali from the system.

In the third aspect of the invention, a continuous process for converting a hydrocarbon feedstock to an alkylamine includes:

(a) the formation of alkyl halides by reacting the molecular halogen with a hydrocarbon feedstock under process conditions sufficient to form alkyl halides (for example ethyl bromide) and hydrogen halide, preferably with almost all the molecular halogen consumed;

(b) the formation of alkylamines and alkali metal halide when the alkyl halides are contacted with ammonia or aqueous ammonia solution under process conditions sufficient to form alkylamines and alkali metal halide;

(c) separating alkylamines from an alkali metal halide;

(d) electrolytic conversion of an alkali metal halide into hydrogen and molecular halogen, whereby the halogen can be reused;

(e) repeating the steps from (a) to (s) the desired number of times.

These steps may be carried out in the order indicated or, alternatively, in a different order. Optionally, the alkyl halides are reproportioned by reacting some or all of the alkyl halides with the feed of alkanes, and the fraction of monohalogenated hydrocarbons present is increased.

In the fourth aspect of the invention, a continuous method for converting coal to coke and hydrogen is proposed, comprising:

(a) the formation of brominated intermediate products for the processing of coal and hydrogen halide in the reaction of ground coal with molecular halogen under process conditions sufficient for bromination and dissociation of the main elements of the skeleton of coal, thereby forming a mixture of brominated intermediate products of coal processing (for example, polybrominated hydrocarbons);

(b) the formation of coke and hydrogen halide in the reaction of brominated intermediate products of coal processing on the catalyst under process conditions sufficient for the formation of coke and hydrogen halide;

(c) separating coke from hydrogen halide;

(d) electrolytic conversion of the hydrogen halide formed in stage (a) and / or stage (b) into hydrogen and molecular halogen, whereby the halogen can be reused;

(e) repeating the steps from (a) to (s) the desired number of times.

These steps may be carried out in the order indicated or, alternatively, in a different order. The resulting coke can be used to generate electricity needed for the process (through burning, generating steam and generating electricity), or to collect and put on sale.

- 3 017229

In the fifth aspect of the invention, a continuous process is proposed for the conversion of coal or hydrocarbons obtained from biomass to polyols and hydrogen, comprising:

(a) the formation of alkyl halides in the reaction of molecular halogen with coal or hydrocarbon obtained from biomass under process conditions sufficient for the formation of alkyl halides and hydrogen halide, preferably with almost complete consumption of molecular halogen;

(b) the formation of polyols and alkali metal halide by contacting the alkyl halides with an aqueous solution of alkali under process conditions sufficient to form polyols and alkali metal halide;

(c) separating the polyols from the alkali metal halide;

(b) electrolytic conversion of the alkali metal halide into hydrogen and molecular halogen, whereby the halogen can be reused;

(e) repeating the steps from (a) to (b) the desired number of times.

These steps may be carried out in the order indicated or, alternatively, in a different order. Optionally, the alkyl halides are reproportioned by reacting some or all of the alkyl halides with the feed of alkanes, and the fraction of monohalogenated hydrocarbons present is increased.

In one important embodiment of the invention, an electrode with oxygen depolarization is used in the electrolyzer, while electrolysis of hydrogen halide gives molecular halogen and water, and electrolysis of alkali metal halide gives molecular halogen and alkali metal hydroxide, rather than hydrogen. The advantage of this embodiment is to significantly reduce the energy consumption of the electrolytic cell (s). In accordance with another aspect of the invention, an improved electrolytic cell provided with an oxygen depolarization electrode is also provided.

Various aspects of the invention have a number of common elements, including: (1) the halogenation of a hydrocarbon feedstock in the presence of molecular halogen to produce hydrogen halide and an oxidized carbon-containing product; (2) the subsequent reaction of oxidized carbon-containing products to produce final products; (3) separation of carbon-containing products from bromine-containing components; (4) electrolysis of the remaining halogen-containing components (eg, HBr, No. 1Br) to form halogen and hydrogen in the electrolytic cell (or, alternatively, use an oxygen depolarization electrode to produce halogen and water or halogen and alkali metal hydroxide instead of hydrogen). The resulting hydrogen can be used to power one or more process components, or it can be compressed and sold for sale.

Traditionally used at present commercial processing of methane, coal and other hydrocarbons produces synthesis gas (CO + H 2 ), which can be converted into more valuable products, such as methanol and linear alkanes. The production of intermediate synthesis gas is extremely expensive, and to obtain useful products, it is necessary to recover almost completely oxidized carbon. The present invention in many aspects exceeds the traditional process involving synthesis gas and has at least the following advantages.

Use of alkyl halide intermediates to produce more valuable products, including fuels and more valuable chemicals.

Decrease in working pressure (for example, ~ 1-5 atm against ~ 80 atm).

Reducing the maximum operating temperature (for example, ~ 50 ° C vs. ~ 1000 ° C).

No need for pure oxygen.

The absence of a reformer with flame heating, which increases safety when used on offshore platforms.

The simplified design of the reactor compared with a complex converter of synthesis gas to methanol.

No need for a catalyst as opposed to catalysts required for reforming and for the synthesis gas conversion.

Reducing the amount of by-products, which facilitates the purification of methanol.

No need to supply steam for reforming.

Hydrogen production on a separate electrode in the form of a relatively pure product.

Bring the reaction to completion at the last stage by removing the products from the reaction vessel.

According to the invention, the molecular halogen used to form alkyl halides is recovered as hydrogen halide and returned to the electrolytic cell, and the alkyl halides are converted to more valuable products. Examples include the conversion of methyl bromide to aromatics and HBg on a zeolite catalyst, as well as the conversion of monoalkyl bromides (for example ethyl bromide) to olefins (for example, ethylene) and HBg on the catalyst. Alternatively, alkyl halides are easily converted to oxygenates, such as alcohols, ethers, and aldehydes. Examples include the conversion of methyl bromide to methanol and NaBr in an aqueous solution of ΟΗαΟΗ, as well as the conversion of dibromomethane to ethylene glycol and No. 1Br to ΝαΟΗ. In yet another embodiment, the implementation of alkyl halides are easily converted into

- 4 017229 amines. Examples include the conversion of bromobenzene to phenol and aniline in aqueous ammonia, as well as the conversion of ethyl bromide in ammonia to ethylamine and No. 1Br.

The invention finds practical application at production facilities for the extraction of oil or gas, such as an offshore oil or gas drilling rig or a wellhead located on land. The continuous processes described herein can be used in conjunction with the extraction of oil and / or gas using electricity generated in-situ to power the electrolytic cell (s).

Brief Description of the Drawings

Various features, implementations, and advantages of the invention will be more readily understood when considered in consideration of the detailed description of the invention, as well as when referring to the accompanying drawings, in which:

in fig. 1 is a schematic diagram of a continuous method for converting hydrocarbon feedstock to higher hydrocarbons according to one embodiment of the invention;

in fig. 2 is a schematic diagram of a continuous method for converting hydrocarbon feedstock to higher hydrocarbons according to another embodiment of the invention;

in fig. 3 is a schematic diagram of a continuous process for converting hydrocarbon feedstock to methanol in accordance with one embodiment of the invention, in which a membrane-type electrolytic cell is used to regenerate molecular bromine;

in fig. 4 is a schematic diagram of a continuous process for converting hydrocarbon feedstock to methanol according to another embodiment of the invention, in which an electrolytic cell of a diaphragm type is used to regenerate molecular bromine;

in fig. 5 is a schematic diagram of a continuous method for converting hydrocarbon feedstock into higher hydrocarbons, in which an oxygen depolarization cathode is provided, according to one embodiment of the invention;

in fig. 6 is a schematic illustration of an electrolytic cell according to one embodiment of the invention;

in fig. 7 is a schematic illustration of a continuous method for converting coal to coke and hydrogen according to one embodiment of the invention;

in fig. 8 is a schematic illustration of a method for converting coal or biomass to polyols and hydrogen according to one embodiment of the invention;

in fig. 9 is a product distribution diagram illustrating the methane bromination selectivity according to one embodiment of the invention;

in fig. 10 is a product distribution diagram illustrating the selectivity of methyl bromide condensation according to one embodiment of the invention;

in fig. 11 is a product distribution diagram illustrating the selectivity of methyl bromide condensation according to another embodiment of the invention.

Detailed Description of the Invention

The present invention provides a chemical method for converting various types of hydrocarbons into more valuable products, such as fuel hydrocarbons, methanol, aromatics, amines, coke and polyols, using molecular halogen to activate C – H bonds into feedstock and electrolysis to convert the the process of hydrohalic acid (hydrogen halide) or halide salts (eg sodium bromide) back to molecular halogen. Non-limiting examples of hydrocarbon species suitable for use in the present invention include alkanes, such as methane, ethane, propane, and even heavier alkanes; olefins; natural gas and other mixtures of hydrocarbons; hydrocarbons derived from biomass; as well as coal. Some refining processes produce light hydrocarbon streams (so-called light fractions), which are typically a mixture of C 1 -C 3 hydrocarbons, which with or without methane can be used as a hydrocarbon feedstock. With the exception of coal, in most cases the hydrocarbon feedstock is essentially aliphatic in nature.

Hydrocarbons are converted into more valuable products by reaction with molecular halogen, as described above. Bromine (Br 2 ) and chlorine (C1 2 ) are preferred, and bromine is most preferred, in part because the overvoltage required for converting Br - to Br2 is significantly lower than that required for converting C1 - to C12 (1.09 V for Br - against 1.36 V for C1 - ). It is implied that fluorine and iodine can be used, but not necessarily with equivalent results. Some of the problems associated with fluorine can probably be resolved by using dilute fluorine streams (for example, fluorine gas transported in a stream of helium, nitrogen, or another diluent). However, it should be expected that condensation of alkyl fluorides with the formation of higher hydrocarbons will require more stringent reaction conditions due to the strength of the fluorine-carbon bond. Similarly, problems associated with iodine (such as the endothermic nature of some reactions involving iodine) can probably be eliminated by carrying out halogenation and / or condensation reactions at elevated temperatures and / or pressures. In general, the use of bromine or chlorine is preferred, while the use of bromine is most preferred.

- 5 017229

The term higher hydrocarbons as used herein refers to hydrocarbons containing more carbon atoms than one or more components of a hydrocarbon feedstock, as well as olefinic hydrocarbons containing the same or more carbon atoms than one or more components of a hydrocarbon feedstock. For example, if a hydrocarbon feedstock is natural gas — usually a mixture of light hydrocarbons with methane predominance and smaller amounts of ethane, propane and butane, and even smaller quantities of hydrocarbons with a longer carbon chain, such as pentane, hexane, etc. - the higher (e) hydrocarbon (s) obtained according to the invention may include C 2 or higher hydrocarbons, such as ethane, propane, butane; C 5 + hydrocarbons; aromatic hydrocarbons, etc .; and possibly ethylene, propylene and / or longer chain olefins. The term light hydrocarbons (sometimes abbreviated to LCNC) refers to C1-C4 hydrocarbons, such as methane, ethane, propane, ethylene, propylene, butanes and butenes, which are generally in a gaseous state at room temperature and atmospheric pressure. Fuel hydrocarbons, as a rule, contain 5 or more carbon atoms and are liquids at room temperature.

As in this description, and in the claims, the chemicals mentioned in the plural include the mentioned substances in the singular, and vice versa, unless the context otherwise indicates. For example, the term alkyl halides includes one or more alkyl halides, which may be the same (for example, 100% methyl bromide) or different (for example, methyl bromide and dibromomethane); the term higher hydrocarbons includes one or more higher hydrocarbons, which may be the same (for example, 100% octane) or different (for example, hexane, pentane and octane).

FIG. 1-5 are schematic diagrams of technological operations, generally reflecting various embodiments of the invention, in which the hydrocarbon feed is allowed to react with molecular halogen (eg, bromine) and converted into one or more more valuable products. FIG. 1 shows one embodiment of a method for producing higher hydrocarbons from natural gas, methane or other light hydrocarbons. Hydrocarbons (for example, natural gas) and molecular bromine are transferred along separate lines 1, 2 to the bromination reactor 3 and allowed to react there. Products (HBg, alkyl bromides, possibly olefins) and, possibly, unreacted hydrocarbons leave the reactor and are transferred via line 4 to condensation reactor 5 to form carbon-carbon bonds (carbon-carbon attachment). Optionally, the alkyl bromides are first sent to a separation unit (not shown), where the monobrominated hydrocarbons and HBg are separated from the polybrominated hydrocarbons, the latter being transferred back to the bromination reactor for reproportionation with methane and / or other light hydrocarbons, as described in application 358.

In the condensation reactor 5, monobromides and possibly other alkyl bromides and olefins in the presence of a condensation catalyst react to form higher hydrocarbons. Non-limiting examples of condensation catalysts are presented in application 358, paragraphs 61-65. The preparation of doped zeolites and their use as catalysts for the formation of carbon-carbon bonds is described in patent publication No. I8 2005/0171393 A1 on p. 4-5, included in this description in its entirety by reference.

HBg, higher hydrocarbons and (possibly) unreacted hydrocarbons and alkyl bromides exit the condensation reactor and are transferred via line 6 to hydrogen bromide absorption unit 7, where hydrocarbon products are separated from HBg by absorption, distillation and / or another suitable separation method. Hydrocarbon products are diverted via line 8 to a product extraction unit 9, in which products are separated — higher hydrocarbons from natural gas residues or other gaseous substances, which are vented through line 10 or, in the case of natural gas or lower alkanes, are recycled and transferred back to bromination reactor. Alternatively, flammable substances can be sent to an energy unit and used to generate heat and / or electricity to power the system.

Aqueous sodium hydroxide or other alkali is transferred via line 11 to the HBr absorption unit, where HBr neutralization and the formation of aqueous sodium bromide occur. The aqueous sodium bromide, along with small amounts of hydrocarbon products and other organic substances, is transferred via line 12 to separation unit 13, in which organic components are separated from sodium bromide by distillation, liquid-phase extraction, flash evaporation or other suitable means. The organics are either removed from the system to the purification unit of separated products, or in the shown embodiment, they return to block 7 the absorption of HBr via line 14 and finally removed from the system via line 8.

The aqueous sodium bromide is transferred from the separation unit 13 of the organic Iabg organic via line 15 to the electrolytic cell 16 with an anode 17 and a cathode 18. The system is equipped with a supply line 19 for adding water, additional electrolyte and / or acid or alkali to adjust the pH. As a cell, it is more preferable to use a series of electrolytic cells, rather than a single cell. Alternatively, several series of cells can be connected in parallel. Non-limiting

- 6 017229 examples of electrolytic cells include diaphragm, membrane, and mercury cells, which can be monopolar or dipolar. The exact material flows for the feed water, electrolyte and other process characteristics will vary depending on the type of cell used. Aqueous sodium bromide is subjected to electrolysis in an electrolytic cell (s) with oxidation of the bromide ion at the anode (2Br - s Br2 + 2e - ) and recovery of water at the cathode (2H2O + 2e - s H 2 + 2OH - ). Aqueous sodium hydroxide is removed from the electrolyzer and sent to the block absorption HBg on line 11.

Bromine and hydrogen obtained in the electrolyzer are extracted, while bromine is recycled and reused in the process. Specifically, wet bromine is transferred via line 20 to desiccant 21, and dry bromine is transferred via line 22 to heater 23, and then via line 2 back to bromination reactor 3. If the amount of water associated with bromine is permissible during bromination and condensation, the desiccant may not be used. The hydrogen produced at the anode of the electrolytic cell can be diverted or more preferably collected, compressed and sent via line 24 to an energy unit, such as a fuel cell or hydrogen turbine. Alternatively, the hydrogen produced may be recovered for sale or other uses. The generated electricity can be used to supply power to various parts of equipment involved in a continuous process, including electrolytic cells.

Exemplary and preferred conditions (eg, catalysts, pressure, temperature, residence time, etc.) of bromination, C – C condensation, reproportionation, product separation, HBg purification, and corrosion resistant materials are presented in application 358 in paragraphs 39-42 ( bromination), 43-50 (reproportionation), 61-65 (C – C condensation), 66–75 (product separation), 82–86 (cleaning HBg and halogen extraction) and 87–90 (corrosion-resistant materials), with the specified paragraphs included in this application in its entirety. Anodes, cathodes, electrolytes, and other signs of an electrolytic cell (s) are selected based on a number of factors understood by a person skilled in the art, such as performance, current power levels, and chemical features of the electrolysis reaction (s). Non-limiting examples are presented in US Pat. Nos. 4,1110180 (Νίάοΐα с1 а1.) And 6368490 (Section 1); Υ. δΐιίιηίζιι. N. Mshta, N. Uataho, Sak-Ryake E1es1go1uk1k oG Nuygosatyos Lai Ikshd RTEE-Vopyy E1es1toye, Ιηΐ. 1. Nygodep Epegdu, Wo1. 13, Νο. 6, 345-349 (1988); Ό. van UeEep, N. apdepkatr, A. MoguoikkeG, R. M111shd1op, HBr E1es1go1uk18 ίη 1ye 1kraga MaGK 13A E1ie Sac EekYryiphaiop Rgosekk: E1es1to1uk1k ίη Eem and Se11 1. Arryey E1es1tosyet1k1gu, Uo1. 20, 60-68 (1990); apy 8. Mo1ira11u, Ό. Mack, E. Egepe, 1. ^ Shepet, Resuidd Syoppe Ggot Nygodep Siotot, Tyje Elys1gosjie1ssa1 8ostelyu 1n1etGas, Ea11 1998, 32-36; All publications are included in this description in its entirety by reference.

In one embodiment of the invention illustrated in FIG. 1, methane is introduced into an ideal displacement reactor made from AESOYA alloy at a rate of 1 mol / s, and molecular bromine is introduced at a rate of 0.50 mol / s, with a total residence time in the reactor of 60 s at 425 ° C. The main hydrocarbon products include methyl bromide (85%) and dibromomethane (14%), and also HBr is formed at a rate of 0.50 mol / s. Methane conversion is 46%. Products are transferred via line 4 to condensation reactor 5, which is a packed bed reactor containing an ion exchange for transition metal (for example, Mn) zeolite condensation catalyst on alumina carrier 28M5 at 425 ° C. In the condensation reactor 5, a certain distribution of higher hydrocarbons is formed, which is determined by the spatial-temporal characteristic of the reactor. In this example, 10 s is the preferred time to produce gasoline products. HBg, higher hydrocarbons and unreacted alkyl bromides (trace amounts) leave the condensation reactor and are transferred via line 6 to hydrogen bromide separation unit 7, where HBg is partially separated by distillation. Aqueous sodium hydroxide is injected and allowed to react at 150 ° C with the formation of sodium bromide and alcohols from HBg and unreacted alkyl bromides. The aqueous and organic components are transferred via line 12 to separation unit 13, in which organic components are separated from sodium bromide by distillation. The aqueous sodium bromide is transferred via line 15 from separation unit No. 1Br-organic to electrolytic cell 16 with anode 17 and cathode 18. To add water, additional electrolyte and adjust pH to values less than 2 by adding acid, feed line 19 is provided. Electrolysis is carried out cell membrane type. Aqueous sodium bromide is subjected to electrolysis in an electrolytic cell with oxidation of the bromide ion at the anode (2Br - ВVg2 + 2e - ) and restoration of water at the cathode (2H2O + 2e - ÜN 2 + 2OH - ). The aqueous sodium hydroxide is removed from the electrolyzer and sent to the HBg absorption unit via line 11. Bromine and hydrogen are produced in the electrolyzer.

FIG. 2 shows an alternative embodiment of a method for converting natural gas, methane, or other types of hydrocarbons into higher hydrocarbons, such as fuel hydrocarbons and aromatics. In this embodiment, the electrolysis takes place in a non-alkaline medium. Products from the condensation reactor (ie, higher hydrocarbons and HBg) are transferred via line 6 to block 7 of HBr absorption, where hydrocarbon products are separated from HBg. After the residual organic components are removed from HBr in separation unit 13, the enriched aqueous solution HBr is transferred

- 7 017229 poured on line 15 into the electrolytic cell 16. Replenishment of water, electrolyte or acid / base to adjust the pH, if necessary, is carried out via line 19. The aqueous solution of HBg is electrolyzed to form molecular bromine and hydrogen. As separation and removal of Br 2 from the electrolyzer, the concentration of HBr in the electrolyzer decreases. The resulting depleted aqueous solution of HBr, along with a certain amount of bromine trapped or dissolved in it (Br 2 ), is transferred via line 25 to column 26 to separate bromine, where bromine (Br 2 ) is separated from the lean aqueous solution of HBg by distillation or another suitable separation operations. The depleted aqueous solution of HBg is transferred back to the block of absorption of HBg via line 27. Moist bromine is transferred via line 28 to desiccant 21, where it is dried.

In another embodiment of this aspect of the invention (not shown), natural gas, methane, or other hydrocarbon feedstock is converted to higher hydrocarbons, and halogen (for example, Br 2 ) is extracted by gas-phase electrolysis of hydrogen halide (for example, HBr). The products from the condensation reactor (i.e., higher hydrocarbons and HBg) are transferred along one more line to the HBr absorption unit, where hydrocarbon products are separated from HBg. After the residual organic components are removed from the HBr in the separation unit, the gaseous HBr is transferred along one more line to the electrolytic cell. Gaseous HBg is subjected to electrolysis with the formation of molecular bromine and hydrogen. Wet bromine is carried along another line to the dryer, where it is dried. Optionally, the desiccant may not be used if dry HBr is fed into the electrolysis cells.

FIG. 3 shows one embodiment of another aspect of the invention in which natural gas, methane, or other hydrocarbon feedstock is converted to methanol through the intermediate methyl bromide. Natural gas and gaseous bromine are transferred along separate lines 201 and 202 to the bromination reactor 203 and allowed to react. The reaction products (for example, methyl bromide and HBr), as well as, possibly, unreacted hydrocarbons, are transferred via line 204 through heat exchanger 205, which lowers their temperature. If necessary, the gases are cooled additionally when passing through the cooler 206. Some of the gases 206 are transferred via line 207 to the absorber 208 HBg. The remainder of the gases, bypassing the absorber HBr, is transferred via line 209 directly to the reactor / absorber 210. The separation proportions are determined by the acid / alkaline disproportionation required to achieve the required pH in the reactor absorber.

Water that may have undergone pre-treatment, for example, in reverse osmosis unit 211 to minimize the salt content, enters the methanol reactor 210 through line 212. In addition, a separate line 213 transfers water to the absorber 208 HBg.

The solution HBr formed in the absorber 208 HBr is sent via line 214 to separation column 215 (where the organics are separated by distillation or other methods), and then sent to the reactor / absorber 210 through line 216. The gases from the absorber HBg are mixed with the bypass flow from the cooler 206 and transferred via line 209 to the reactor / absorber 210. The solution NVB from separation column 215 is transferred via line 217 to the storage tank 218 NVB.

Aqueous sodium hydroxide (for example, 5-30 wt.%) Enters the methanol reactor 210 through line 219. A weak solution No. 1Br in water is also fed to the methanol reactor 210 via line 220.

In the methanol formation reactor, methyl bromide reacts with water in the presence of a strong base (sodium hydroxide), and methanol is formed, along with possible by-products such as formaldehyde or formic acid. A liquid stream containing methanol, by-products, aqueous sodium bromide and aqueous sodium hydroxide is withdrawn from the reactor via line 221 to the separation column 222. Part of the bottom liquid from the reactor / absorber 210 through line 223 is forced to circulate through cooler 224 to regulate the temperature in the reactor / absorber 210.

The separation column 222 is equipped with a reboiler 225 and possibly works with partial reflux. The aqueous sodium bromide and sodium hydroxide are removed along with most of the water as a stream of bottoms from the separation column. The vapors leaving the top of the separation column are transferred via line 226 to another distillation unit 227, equipped with a reboiler 228 and a condenser 229. In distillation unit 227, by-products are separated from methanol, and methanol is removed from distillation unit 227 via line 230, through cooler 231 to storage tank 232. The vapors from distillation unit 227 (containing by-products) are transferred via line 233 through condenser 229, and then through line 234 to reservoir 235 for storing by-products. Optionally, depending on the particular by-products obtained and their boiling points, methanol can be separated as a distillate, while the by-products are isolated as a bottoms residue.

The waste stream removed from distillation unit 222 and reboiler 225 contains water and aqueous sodium bromide and sodium hydroxide. This stream is withdrawn from the distillation unit through line 236 and cooled as it passes through chiller 237 before being supplied to sodium bromide storage tank 238. It is advisable to lower the pH of this saline solution. This is achieved by measuring the supply of aqueous HBg from the storage tank for hydrogen bromide via line 239 to a pH control device 240 connected to a storage tank 238 for sodium bromide.

- 8 017229

After adjusting the pH of the sodium bromide in the storage tank 238 to the desired level (for example, to slightly acidic), the aqueous sodium bromide is removed from the tank and transferred along line 241 through a filter 242 and fed to an electrolytic cell 243 with an anode 244 and cathode 245. The filter is designed to protect membranes in electrolytic cells. Preferably, a series of electrolytic cells, rather than a single cell, is used as the cell.

Aqueous sodium bromide is subjected to electrolysis in an electrolytic cell (s) with oxidation of the bromide ion at the anode (2W - ^ W2 + 2e - ) and recovery of water at the cathode (2H2O + 2e - ^ H 2 + 2OH - ). This leads to the formation of sodium hydroxide, which is removed from the electrolyzer in the form of an aqueous solution through line 246 to storage tank 247. Then the sodium hydroxide solution is sent to the methanol reactor 210 through line 219.

Molecular bromine is removed from the electrolyzer through line 248 to compressor 249, and then to desiccant 250. Bromine is returned to the bromination reactor 203 after passing through heat exchanger 205 and, if necessary, through heater 251. Molecular bromine dissolved in the anolyte is also removed from the electrolytic cells (cells) 243, transferring the anolyte from the cell (cells) through line 252 to separation column 253, where the bromine is removed by distillation with natural gas (supplied through line 254) or by other means. Molecular bromine is transferred via line 255 to compressor 249, dryer 250, etc. before returning to the bromination reactor as described above.

The hydrogen produced in the electrolyzer is discharged through line 256, compressed in compressor 257, and possibly sent to energy block 258. Residual methane or other inert gases can be removed from methanol production line 259. Methane or natural gas can be sent to energy block 258 to increase energy production. If necessary, additional natural gas or methane may be fed to this unit via line 260.

In the laboratory implementation of the elements of the process shown in FIG. 3, methane was reacted with bromine gas at 450 ° C in a bromination reactor in the form of a glass tube with a passage time of 60 s. The products are methyl bromide, HBr and dibromomethane with methane conversion of 75%. In the methanol formation reactor, methyl bromide, HBr, and dibromomethane react with water in the presence of sodium hydroxide to form methanol and formaldehyde (from dibromomethane). Further, it is shown that formaldehyde is disproportioned to methanol and formic acid. Therefore, in general, the products are methanol and formic acid.

During the process shown in FIG. 3, membrane-type electrolytic cells are used, and not diaphragm-type cells. In the membrane cell, sodium ions with only a small amount of water flow into the cathode chamber. In contrast, in the cell of the diaphragm type, sodium ions and water enter the cathode chamber. In an alternative embodiment of the invention shown in FIG. 4, diaphragm cells are used, which leads to continuous depletion of the anolyte at No. 1Br. To replenish the NaBr content, the depleted anolyte is taken through line 252 to separation column 253, where bromine is distilled off and transferred to compressor 249, and then to desiccant 250. Solution NaW from separation column 253 is transferred via line 270 to storage tank 238 No. Вг. where it is mixed with a richer # 1G solution. Other features of the process are similar to those shown in FIG. 3

In another aspect of the invention, molecular halogen is recovered by electrolysis using a non-hydrogen cathode, i.e. cathode with oxygen depolarization, which significantly reduces energy consumption by obtaining water instead of hydrogen. FIG. 5 shows one embodiment of this aspect of the invention; in this case we are talking about getting higher hydrocarbons. The process diagram is similar to that shown in FIG. 1, with the differences described below.

Bromine and natural gas, methane or another light hydrocarbon are forced to react in the bromination reactor 303 and then in the condensation reactor 305. Organics and HBg are separated in block 307 of HBr absorption. The aqueous sodium bromide is transferred via line 315 to an electrolytic cell 316 equipped with an anode 317, a cathode 318 with oxygen depolarization, and a nozzle or an oxygen inlet line 324. It is possible that, along line 319, additional water or electrolyte, or chemicals for pH adjustment, are transferred to the cell.

Molecular bromine is released at the anode (2W - ^ W2 + 2e - ), and the wet bromine is transferred via line 320 to desiccant 321, through heater 323, and then sent back to the bromination reactor 303. At the cathode, electrolytic reduction of oxygen occurs in the presence of water (1 / 2O2 + H 2 O + 2e - ^ 2OH - ), and hydroxyl ions are removed as aqueous sodium hydroxide through line 311 to HBg absorption unit 307.

The invention also provides an improved electrolytic cell for converting halides to molecular halogen, one embodiment of which is shown in FIG. 6. The cell 400 includes a gas distribution manifold 401 through which gaseous oxygen, air or oxygen-enriched air can be introduced; gas diffusion cathode 402, which is permeable to oxygen (or oxygen-containing gas); cation exchange membrane 403; cathode electrolyte chamber 404 located between the cation-exchange membrane and gas diffusion

- 9 017229 ny cathode; an anode electrolyte chamber 405 and an anode 406 extending into the anode electrolyte chamber. When working in an alkaline (primary) environment, water is introduced into the cathode electrolyte chamber through the opening 407, and aqueous sodium hydroxide is withdrawn from this chamber through another opening 408. Similarly, aqueous sodium bromide is introduced into the anode electrolytic chamber through the opening 409, and molecular bromine is removed from the anode electrolyte chamber through line 410. The anode and cathode can be connected to a power supply (not shown), which may include equipment for converting alternating current to direct current (for example, mechanical (electrocontact) rectifier, generator-motor unit, semiconductor rectifier, synchronous converter, etc.) and other components.

In operation, water is introduced into the cathode electrolyte chamber through the water inlet 407, and aqueous sodium bromide is introduced into the anode electrolyte chamber 405 through the opening 409. Oxygen is supplied through the gas distribution manifold 401 and the cell is powered on. Sodium bromide is reduced at the anode, bromine gas released during this process is removed via line 410, and sodium ions are transferred through the cation-exchange membrane to the cathode electrolyte chamber. At the cathode, electrolytic reduction of oxygen to hydroxyl ion occurs in the presence of water. The aqueous sodium hydroxide leaves the cathode electrolyte chamber through the opening 408.

The electrolytic cell described herein can be used in combination with various processes, including the embodiments described above. Its use is particularly preferred where it is important to reduce energy consumption and undesirable release of hydrogen (for example, where special fire protection measures are required, for example, on offshore drilling rigs).

Although the invention can be applied in various industrial processes, it is of particular value where the continuous production process described here, for example, higher hydrocarbons or methanol, is carried out on an offshore oil drilling rig, or drilling platform, or on an object located on shore in a remote place. Part of the utility of the invention is the conversion of a material that is difficult to transport (for example, natural gas) into a more easily transportable liquid material, such as higher hydrocarbons or methanol. In addition, the utility of the invention is to use existing at the production facility electrogenerating power, such as an electric generator or other power source.

According to one embodiment of this aspect of the invention, an improved production facility is proposed in which oil or gas is pumped out of a well and thus removed from the ground, wherein said facility has an electric generator or other source of electrical supply, and the improvement includes:

(a) the formation of alkyl halides by reacting the molecular halogen with oil or gas pumped out of the well, under process conditions sufficient to form alkyl halides and hydrogen halide, optionally with almost complete consumption of molecular halogen;

(b) the formation of higher hydrocarbons and hydrogen halide by contacting the alkyl halides with the first catalyst under process conditions sufficient to form higher hydrocarbons and hydrogen halide;

(c) separating higher hydrocarbons from hydrogen halide;

(b) electrolytic conversion of hydrogen halide into hydrogen and molecular halogen using electrical energy provided by an electric generator or electrical power source, whereby the halogen can be reused.

In another embodiment, an improved production facility is proposed in which oil or gas is pumped out of a well and thus removed from the ground, wherein said object has an electric generator or other source of electrical supply, and the improvement includes:

(a) the formation of alkyl halides by reacting a molecular halogen with a hydrocarbon feedstock under process conditions sufficient to form alkyl halides and hydrogen halide, optionally with almost complete use of molecular halogen;

(b) the formation of methanol and an alkali metal halide when the alkyl halides are contacted with an aqueous alkali under process conditions sufficient to form methanol and an alkali metal halide;

(c) separating methanol from an alkali metal halide;

(b) electrolytic conversion of hydrogen halide into hydrogen, molecular halogen, and aqueous alkali using electrical energy provided by an electric generator or electrical power source, whereby halogen and alkali can be reused.

In another aspect of the invention, the general approach outlined above, including the steps of halogenation, product formation, product separation, and electrolytic halogen regeneration, is used to produce alkylamines. Thus, in one embodiment, the implementation of natural gas, methane or other aliphatic hydrocarbon feedstock is converted into alkylamines through intermediate alkyl bromides.

- 10 017229

Raw materials and gaseous bromine are transferred along separate lines to the bromination reactor and allowed to react. Bromination products (for example, methyl bromide and HBg) and possibly unreacted hydrocarbons are transferred along another line through a heat exchanger, which lowers their temperature. Alkyl bromides are then transferred along one more line to the amination reactor. Ammonia or ammonia water is fed to the amination reactor in a separate line. The alkyl bromide and ammonia are allowed to react under process conditions sufficient to form alkylamines (eg, например 2 ) and sodium bromide, which are then separated in a manner similar to that described above with respect to methanol production. Aqueous sodium bromide is transferred along one more line to the electrolytic cell or cells, where it is electrolytically converted to hydrogen and molecular bromine, which allows reuse of bromine in the next cycle.

FIG. 7 and 8, two other aspects of the invention are presented in which coal is converted into more valuable coke, or coal or biomass is converted into more valuable polyols (polyalcohols), and the halogen used in the process is regenerated electrolytically. In the embodiments shown in FIG. 7, the crushed coal is allowed to react with molecular bromine at elevated temperature with the formation of coke, HBr, and armored intermediates of coal treatment (C x Br p ). Brominated coal processing intermediates are converted to coke, allowing them to come into contact with the catalyst, and additional hydrogen bromide is formed. Then coke and hydrogen bromide are separated, then hydrogen bromide is transferred along one more line to the electrolytic cell or cells, similar to those described above, whereby molecular bromine can be regenerated and reused.

FIG. 8 shows a similar process in which coal or hydrocarbons obtained from biomass are brominated to form alkyl bromines or alkyl bromides and HBg, which are then treated in a manner similar to the one described above, for example alkyl bromides and HBg, at least partially separated, and allowed to alkyl bromides to react with alkali (for example, sodium hydroxide), resulting in the formation of sodium bromide, water and polyalcohols (C X H Y-H (OH) H ). The polyalcohols are separated from sodium bromide and the aqueous sodium bromide is transferred along one more line to the electrolytic cell or cells, where molecular bromine is regenerated and subsequently separated and reused.

The following non-limiting examples illustrate various embodiments or features of the invention, including methane bromination; C – C condensation to form higher hydrocarbons, for example, light olefins and aromatics (benzene, toluene, xylenes (BTH)); hydrolysis of methyl bromide to methanol; hydrolysis of dibromomethane to methanol and formaldehyde, followed by disproportionation to formic acid.

Example 1. Methane bromination.

Methane (11 st.sm 3 / min, 1.0 atm) was combined with nitrogen (15 st.sm 3 / min, 1.0 atm) at room temperature in the T-shaped mixer and passed through a bubbler filled with bromine at 18 ° WITH. A mixture of CH 4 A 2 / Br 2 was passed into a pre-heated glass tube (inner diameter 2.29 cm, length 30.48 cm, filled with glass granules) at 500 ° C, where methane bromination occurred with a residence time of 60 s, with the main result being bromomethane, dibromomethane and HBg

CH, + Br 2 CH 3 Br + CH 2 Br 2 + HBg.

As the products left the reactor, they were collected using a series of traps containing | M No. UN. neutralizing HBr; and hexadecane (containing octadecane as an internal standard) to dissolve as much of the hydrocarbon products as possible. Volatile components, such as methane, were collected in a gas bag after HBg / hydrocarbon traps.

After the completion of the synthesized reaction, coke or carbon deposits were burned in a stream of heated air (5 cm 3 / min) at 500 ° C for 4 hours and CO 2 was captured with a saturated solution of barium hydroxide in the form of barium carbonate. Quantitative analysis of all products was performed by gas chromatography (GC). The amount of coke was determined by the amount of CO 2 released during coking. The results are presented in FIG. 9.

Example 2. Condensation of CH 3 Br to light olefins.

2.27 g of magnesium-doped (Md) 5% zeolite Ζ8Μ-5 (SVU8014) was loaded into a tubular quartz reactor (inner diameter 1.0 cm), preheated to 400 ° C before the start of the reaction. CH 3 Vg, diluted with Ν 2 , was pumped into the reactor at a flow rate of 24 μl / min for CH 3 Vg, regulated using a liquid micropump, and 93.3 ml / min for 2 . At these established costs, the condensation reaction of CH 3 Vg occurred above the catalyst bed with a residence time of 0.5 s and a partial pressure of CH 3 Vg of 0.1.

After 1 h of reaction, the products left the reactor and were collected using a series of traps containing 4 M NOH, neutralizing HBr, and hexadecane (containing octadecane as an internal standard) to dissolve as much of the hydrocarbon products as possible. Volatile components, such as methane and light olefins, were collected in a gas bag after HBg / hydrocarbon traps.

- 11 017229

After the completion of the condensation reaction, coke or carbon deposits were burned in a stream of heated air (5 cm 3 / min) at 500 ° C for 4 hours, and CO 2 was captured with a saturated solution of barium hydroxide in the form of barium carbonate. Quantitative analysis of all products was performed by GC. The amount of coke was determined by the amount of CO 2 released during coking. The results are presented in FIG. ten.

Even with such a short residence time, the conversion of CH 3 Vg reached 97.7%. Among the condensation products, the main products are C 3 H 6 and C 2 H 4 , their sum made a 50% contribution to carbon yield. BTX (benzene, toluene, xylenes), other hydrocarbons, brominated hydrocarbons, and a small amount of coke constituted the remainder of the converted carbon.

Example 3. Condensation of CH 3 Vg to BTX.

The Μη-ion-exchange zeolite Ζ8Μ-5 (SVU3024, 6 cm long) granules were loaded into a tubular quartz reactor (inner diameter 1.0 cm), previously heated to 425 ° С before the start of the reaction. CH 3 Vg, diluted with Ν 2 , was pumped into the reactor at a flow rate of 18 μl / min for CH 3 Vg, regulated using a liquid micropump, and 7.8 ml / min for 2 . At these established costs, the condensation reaction of CH 3 Vg occurred above the catalyst bed with a residence time of 5.0 s and a partial pressure of CH 3 Vg of 0.5.

After 1 h of reaction, the products left the reactor and were collected using a series of traps containing 4 M No. 1OH. neutralizing HBr; and hexadecane (containing octadecane as an internal standard) to dissolve as much of the hydrocarbon products as possible. Volatile components, such as methane and light olefins, were collected in a gas bag after HBg / hydrocarbon traps.

After the completion of the condensation reaction, coke or carbon deposits were burned in a stream of heated air (5 cm 3 / min) at 500 ° C for 4 hours, and CO 2 was captured with a saturated solution of barium hydroxide in the form of barium carbonate. Quantitative analysis of all products was performed by GC. The amount of coke was determined by the amount of CO2 released during the coke removal. The results are presented in FIG. eight.

In this mode of operation for maximum BTX output, CH 3 Vg can be fully converted. Output BTX reached 35.9%. The contribution of other hydrocarbons, aromatics, brominated hydrocarbons and coke to carbon yield was 51.4, 4.8, 1.0 and 6.9%, respectively. The main component of other hydrocarbons is propane, and it can be returned to the system for reproportionation followed by further condensation to further increase the overall yield of BTX.

Example 4. Alkaline hydrolysis of bromomethane to methanol

СЩВг + ИАОН СН 3 ОН + ИАВт

13.2 g of a 1 M aqueous solution of sodium hydroxide (13.2 mmol) and 1.3 g of bromomethane (12.6 mmol) were successively introduced into a reactor with a vapor localization (30 V) stainless steel with a capacity of 30 ml equipped with a magnetic stirrer. The reactor was carefully purged with nitrogen to remove air from the top of the reactor before closing the lid. The closed reactor was placed in an aluminum heating unit, preheated to 150 ° C, to immediately start the reaction. The reaction was carried out for 2 hours at this temperature with stirring.

After termination of the reaction, the reactor was placed in an ice bath at the initial moment to cool the products inside. After opening the reactor, the reaction liquid was transferred to a vessel and diluted with cold water. The vessel was connected to a gas bag used to collect unreacted methyl bromide, if any. The reaction liquid was weighed and analyzed the concentration of products by gas chromatography with FID (flame ionization detector) on a capillary column adapted to enter the water sample.

Analysis of the gaseous product indicates that no residual methyl bromide was present, indicating that the methyl bromide was completely converted. Based on the concentration measurements in the liquid product, the calculated yield of methanol, including trace amounts of dimethyl ether, was 96%.

Example 5. Alkaline hydrolysis of dibromomethane to formaldehyde, followed by disproportionation to methanol and formic acid

СН 2 Вг 2 + 2KaON - »НСНО + 2КаВг + Н 2 О

NSNO + 1 / 2H 2 O -> 1 / 2CH 3 OH + 1 / 2SSN

Alkaline hydrolysis of dibromomethane was carried out according to the same procedure as in Example 5, with the difference that the high ratio No. 1OH / CH 2 Br 2 (2.26) was used. After collecting the reaction liquid, a sufficient amount of a concentrated solution of hydrogen chloride was added to neutralize excess sodium hydroxide and acidify sodium formate. It was noted that methanol and formic acid were the only products, which indicated that, following hydrolysis to methanol and formaldehyde, formaldehyde completely disproportionated to (additional) methanol and formic acid occurred. GC analysis showed that the conversion of dibromomethane reached 99.9%; at the same time, the yields of methanol and formic acid reached 48.5 and 47.4%, respectively.

- 12 017229

Examples 4 and 5 demonstrate that complete hydrolysis of bromomethane to methanol is possible, as well as complete hydrolysis of dibromomethane to methanol and formic acid under weakly alkaline conditions. The results are presented in the table.

Alkaline hydrolysis of CH 3 Vg and CH 2 Vg 2 followed by disproportionation of NSNO

Original form
SNZVg SN.Vg,
IaOH / SNzVg or CH 2 Vg 2 1.05 2.17
Temperature (° С) 150 150
Reaction time (s) 2 2
Conversion (%) 100.0 99.9
Output SNSON (%) 96.0 48.5
The output of NSAF (%) 47.4

The invention has been described with reference to various representative and preferred embodiments, but is not limited to them. Other modifications and equivalent arrangements that will be apparent to those skilled in the art upon consideration of this disclosure are also included in the scope of the invention.

As one example, molecular bromine can also be removed from an electrolytic cell (s) using a competitive extraction method that uses an inert organic solvent, such as chloroform, carbon tetrachloride, ether, and the like. The solvent is injected on one side of the cell; bromine is distributed between the organic and aqueous phases; the solvent loaded with bromine is removed from the other side of the cell. Further, bromine can be separated from the solvent by distillation or another suitable method, and then returned back to the system for reuse. Distribution contributes to a significantly higher solubility of bromine in solvents such as chloroform and carbon tetrachloride, compared with solubility in water. Extraction in this way serves a dual purpose: it separates Br 2 from other forms of bromine that may be present (for example, Br - , Ovg - , which are insoluble in the organic phase); and it allows you to concentrate bromine and easily separate it from the organic phase (for example, by distillation). The optimum pH during extraction (as well as for separating bromine by heating bromine-containing aqueous solutions in a gas stream) is 3.5, the pH at which the concentration of molecular bromine (Br 2 ) is maximum compared to other forms of bromine.

As another example of modifications of the method described in the present invention, various pumps, faucets, heaters, coolers, heat exchangers, control units, power supplies and other equipment can be used to optimize the processes in addition or alternatively to those shown in the figures. Additionally, in the practical implementation of the present invention it is possible to use other features and implementation options, such as those described in application 358 or elsewhere. The invention is limited only by the attached claims and their equivalents.

Claims (13)

  1. CLAIM
    1. A continuous method for the conversion of hydrocarbons into higher hydrocarbons, including:
    (a) reacting molecular halogen with a hydrocarbon feedstock to form alkyl halides and hydrogen halide;
    (b) contacting alkyl halides with a catalyst to form higher hydrocarbons and hydrogen halide;
    (c) separating higher hydrocarbons from hydrogen halide;
    (b) electrolytic conversion of hydrogen halide to hydrogen and molecular halogen;
    (e) repeating the steps from (a) to (b) the desired number of times, with the molecular halogen from step (b) being used in the repeated step (a).
  2. 2. The continuous method of claim 1, wherein the hydrocarbon feed contains natural gas.
  3. 3. The continuous process of claim 1, wherein the hydrocarbon feed contains methane.
  4. 4. The continuous process according to claim 1, wherein step (b) is carried out in an aqueous medium.
  5. 5. A continuous process according to claim 1, wherein step (b) is carried out in the gas phase.
  6. 6. The continuous method of claim 1, wherein the higher hydrocarbons contain fuel hydrocarbons and / or aromatic hydrocarbons.
  7. 7. The continuous process according to claim 6, wherein the aromatic hydrocarbons contain benzene, toluene, and xylenes.
  8. 8. The continuous method according to claim 1, wherein step (b) comprises electrolytic conversion of hydrogen halide into hydrogen and molecular halogen using an electrolytic cell including
    - 13 017229 gas distribution manifold, through which you can enter the gaseous oxygen, air or oxygen-enriched air;
    gas diffusion cathode, which is permeable to oxygen or oxygen-containing gas; cation exchange membrane;
    a cathode electrolyte chamber located between the cation-exchange membrane and the gas diffusion cathode;
    anode electrolyte chamber and anode extending into the anode electrolyte chamber.
  9. 9. The continuous method of claim 1, wherein the hydrocarbon feed contains oil or gas pumped from a well at an oil or gas production facility, wherein the hydrogen halide is converted to hydrogen and molecular halogen using electrical energy provided by an electric generator or electrical supply source.
  10. 10. The continuous method of claim 9, wherein the oil and gas production facility is located on the shelf.
  11. 11. The continuous method of claim 9, wherein step (b) comprises electrolytically converting hydrogen halide to hydrogen and molecular halogen using electrical energy provided by an electric generator or power supply source using an electrolytic cell including a gas distribution manifold through which it can be introduced gaseous oxygen, air or oxygen-enriched air;
    gas diffusion cathode, which is permeable to oxygen or oxygen-containing gas; cation exchange membrane;
    a cathode electrolyte chamber located between the cation-exchange membrane and the gas diffusion cathode;
    anode electrolyte chamber and anode extending into the anode electrolyte chamber.
  12. 12. The continuous method according to claim 1, wherein step (b) comprises electrolytic conversion of hydrogen halide into water and molecular halogen in an electrolytic cell or cells equipped with an oxygen depolarization cathode.
  13. 13. The continuous method of claim 12, wherein the electrolytic cell comprises a gas distribution manifold through which gaseous oxygen, air or oxygen-enriched air can be introduced;
    gas diffusion cathode, which is permeable to oxygen or oxygen-containing gas; cation exchange membrane;
    a cathode electrolyte chamber located between the cation-exchange membrane and the gas diffusion cathode;
    anode electrolyte chamber and anode extending into the anode electrolyte chamber.
    Electrolytic cells
    Desiccant
    Condensation / Water IaVg
    Water ΝβΟΗ / ΝβΒΓ
    Dry Bromine (Ventilation)
    Cooler
    Product recovery
    Product
    Separation
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