WO2008100170A1 - Procédé de fabrication de méthanol et installation correspondante - Google Patents

Procédé de fabrication de méthanol et installation correspondante Download PDF

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Publication number
WO2008100170A1
WO2008100170A1 PCT/RU2007/000070 RU2007000070W WO2008100170A1 WO 2008100170 A1 WO2008100170 A1 WO 2008100170A1 RU 2007000070 W RU2007000070 W RU 2007000070W WO 2008100170 A1 WO2008100170 A1 WO 2008100170A1
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WO
WIPO (PCT)
Prior art keywords
reaction
refrigerant
gas
containing gas
reaction mixture
Prior art date
Application number
PCT/RU2007/000070
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English (en)
Russian (ru)
Inventor
Aleksey Mikhailovich Shkoda
Vladimir Sergeevich Arutiynov
Viktor Viktorovich Plyonkin
Valery Mikhailovich Rudakov
Valery Ivanovich Savchenko
Sergey Evgenievich Chaika
Original Assignee
Aleksey Mikhailovich Shkoda
Vladimir Sergeevich Arutiynov
Viktor Viktorovich Plyonkin
Valery Mikhailovich Rudakov
Valery Ivanovich Savchenko
Sergey Evgenievich Chaika
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aleksey Mikhailovich Shkoda, Vladimir Sergeevich Arutiynov, Viktor Viktorovich Plyonkin, Valery Mikhailovich Rudakov, Valery Ivanovich Savchenko, Sergey Evgenievich Chaika filed Critical Aleksey Mikhailovich Shkoda
Priority to PCT/RU2007/000070 priority Critical patent/WO2008100170A1/fr
Publication of WO2008100170A1 publication Critical patent/WO2008100170A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only

Definitions

  • the invention relates to the field of organic chemistry, and in particular to a technology for producing methanol by direct oxidation of a hydrocarbon-containing gas - natural, associated gas, oil refining production, and can be used in the chemical, petrochemical, oil and gas industries.
  • hydrocarbon-containing gases which are environmentally friendly fuel and valuable chemical raw materials
  • More technologically advanced is the use of liquid hydrocarbon products, in particular methanol, as a universal fuel and the initial product of many chemical industries.
  • oil and gas producers themselves need large volumes of methanol to be used as a means of preventing the formation of hydrates in gaseous media during the extraction and transportation of hydrocarbon gases.
  • a known method of producing methanol from methane-containing natural gas comprising mixing natural gas with air or oxygen, supplying these gases to an inert surface reactor and their interaction at elevated pressures of 1-10 MPa, elevated temperatures of 300-400 0 C, with an initial oxygen concentration of 2-20% in the mixture and a reaction time of 2-1000 s in the absence of any additional materials in the reaction zone that significantly affect the selectivity of the reaction or the yield of products, followed by the release of methanol from the reaction gas and directing unreacted methane to a similar process or recycling it to the reactor.
  • a known method for the production of methanol comprising separately supplying compressed and heated hydrocarbon-containing gas and compressed oxygen-containing gas to the mixing zones of successive reactors, followed by gas-phase oxidation of the hydrocarbon-containing gas in successive reaction zones of reactors at an initial temperature of up to 500 0 C, pressure up to 10 MPa and oxygen content not more than 6 vol.
  • the closest technical solution is a method for the production of methanol, including the separate supply of sequentially compressed and heated hydrocarbon-containing gas and compressed oxygen-containing gas to the mixing zone of the reactor, subsequent gas-phase oxidation of the hydrocarbon-containing gas at an initial temperature of up to 500 0 C, pressure up to 10 MPa and oxygen content no more than 8 about.
  • This method of methanol production compares favorably with others in the possibility of obtaining a higher degree of methane conversion per pass through the use of several reactors in series, a higher selectivity for methanol formation and the ability to avoid soot formation by cooling the reaction mixture before each subsequent oxidation step.
  • the disadvantage of this method is the complex design of the reactor, including a gas-gas heat exchanger to remove a large amount of heat before each subsequent oxidation stage, which makes the whole process expensive and metal-intensive.
  • the large thermal inertia of the heat exchange equipment makes the process difficult to control.
  • adverse catalytic reactions occurring on the walls of the reactor and leading to a decrease in the yield of the target product, methanol, as well as to additional heating of the walls of the reactor have a strong negative effect on the process.
  • the reaction mixture is either heated to temperatures above 600 0 C, which leads to intensive soot formation and a decrease in the yield of the target product as a result of its thermal decomposition in the reactor itself, or heating is limited by a serious complication of the design reactor due to the inclusion of intermediate heat exchangers.
  • the optimal temperature of the gas-phase oxidation process is 520-570 0 C.
  • the indicated catalytic effect manifests itself not only on the wall surface made, for example, of stainless steel, but also on walls made of relatively inert materials, which are sometimes proposed to be used as a coating of the inner walls of a reactor, for example, quartz ( US 4,618,732, Bl).
  • the catalytic reaction of deep oxidation which, in comparison with the gas-phase reaction, forms methanol, has a much greater thermal effect, intense on the walls of the reactor and more intense in the wall layer containing active particles diffusing from the surface of the walls, leads to additional heating of the surface of the reactor and its corrosion, which leads to tightening requirements for the choice of material and leads to a rise in the cost of the reactor.
  • the aim of the invention is to simplify the design and reduce the metal consumption of the reactor, reduce corrosion of the inner surface of the walls of the reactor, increase safety and control process, eliminate the formation of by-products and increase the yield of the target product.
  • the task was to maintain the temperature of the reaction mixture in the desired temperature range at the desired ratio of hydrocarbon-containing gas and oxidizing agent in the reaction mixture, as well as to reduce the concentration of corrosive substances on the inner surface of the walls of the reactor, to reduce the temperature of the walls of the reactor and the stresses of the reactor material by limiting the supply heat to the reaction mixture during the processes of its oxidation and exclude contact of the hot reaction mixture with the internal the surface of the walls of the reactor.
  • the problem was solved by creating a method for the production of methanol, which is carried out sequentially: mixing separately supplied starting reagents: sequentially compressed and heated carbohydrate containing gas and compressed oxygen containing gas, gas-phase oxidation of a hydrocarbon-containing gas at elevated temperature and pressure up to 10 MPa and subsequent cooling of the reaction mixture in the formed, respectively, mixing, reaction zone and cooling zone, and then cooled the resulting mixture containing methanol, methanol is separated, and the exhaust gases are sent to the source hydrocarbon-containing gas or for utilization, characterized in that the cooling zone
  • the reaction mixture is formed by supplying refrigerant in the direction of movement of the reaction mixture stream after the reaction mixture leaves the mixing zone, with the formation of a refrigerant stream having a space inside the stream to accommodate at least part of the reaction zone, and in this part of the reaction zone inside the refrigerant stream maintains the temperature of the reaction mixture in the range from 520 to 600 0 C.
  • the temperature of the reaction mixture inside the refrigerant stream preferably in the range of 520-57O 0 C.
  • reaction mixture it is advisable to subject the reaction mixture repeatedly to sequentially mixing with separately supplied compressed oxygen-containing gas, to gas-phase oxidation and cooling in repeatedly mixing, reaction and cooling zones, and in this case to supply the original compressed and heated hydrocarbon-containing gas to the first of the mixing zones, and oxygen-containing gas to be supplied to each of the mixing zones
  • At least one reactor having a housing in which at least one reaction module is placed, in which are formed in series:
  • a mixing zone adapted for mixing the feed products fed to the module and forming a reaction mixture stream
  • reaction zone for accommodating a stream of a reaction mixture subjected to gas phase oxidation
  • a cooling zone adapted to accommodate at least a portion of the reaction mixture stream within the refrigerant stream in the direction of movement of the reaction mixture stream and configured to vary the flow rate of the refrigerant to ensure the temperature of the reaction mixture is not higher than 600 0 C, and comprising a device for measuring temperature in the reaction zone in the region to the cooling zone and the temperature in the part of the reaction zone located inside the refrigerant stream; a system for preparing a source hydrocarbon-containing gas, providing the possibility of its sequential compression to 1.0-10.0 MPa and heating to 300-5OO ° C, and feeding it into the mixing zone of the reaction module; a system for preparing an oxygen-containing gas, providing the possibility of its compression up to 1.0-10.0 MPa, and feeding it into the mixing zone of the reaction module;
  • a system for supplying refrigerant to the cooling zone comprising a device for supplying the refrigerant in a continuous stream with the formation of a space inside the stream to accommodate at least part of the reaction zone, and configured to control the parameters of the refrigerant stream;
  • the refrigerant supply system in the cooling zone contains several devices that provide the supply of refrigerant in a continuous stream with the formation of a space inside the stream to accommodate at least part of the reaction zone, and configured to control the parameters of the refrigerant stream;
  • the system for supplying refrigerant to the cooling zone can be equipped with a device for generating a flow of refrigerant in the form of a hollow cylinder.
  • the reactor contains several reaction modules placed sequentially in the vessel one after the other.
  • the installation be adapted for use as a refrigerant part of the original cold hydrocarbon-containing gas or a cooled off-gas hydrocarbon-containing gas or an aqueous solution of organic by-products formed after methanol or vapor-gas mixture of an aqueous solution of organic by-products with the original hydrocarbon-containing gas is isolated or gas-vapor mixture of an aqueous solution of organic by-products with chilled waste levodorodsoderzhaschim gas.
  • the method for producing methanol according to the invention can be carried out in a plant according to the invention, for example, shown in FIG. 1, comprising a reactor 1 in which two reaction modules 2-1 and 2-2 are placed in series one after another, each of which has mixing zones 3-1 and 3-2, cooling zones 4-1 and 4-2 of the reaction mixture and reaction zones 5-1 and 5-2, respectively,
  • the mixing zone 3-1 is adapted to receive and mix the starting products supplied to the reaction module 2-1: a sequentially compressed and heated hydrocarbon-containing gas and an initial compressed oxygen-containing gas.
  • the mixing zone 3-2 is adapted to receive and mix the reaction products supplied to the reaction module 2-2 from the reaction module 2-1 and additionally compressed oxygen-containing gas supplied to the reaction module 2-2.
  • the compression, heating and supply of hydrocarbon-containing gas can be performed in a system containing, for example, pipelines 6 for supplying gas from a gas source, a compressor 7 for compressing gas, a gas distribution manifold 8, a heat exchanger 9, in which heat leaving the reactor is used for heating 1 oxidation products, and a pipe 10 for supplying a heated hydrocarbon-containing gas to the reactor 1
  • Compression and supply of oxygen-containing gas can be carried out using a system containing a compressor 11 and pipelines 12-1 and 12-2.
  • the mixing zones 3-1 and 3-2 are also adapted for forming at the outlet of each mixing zone a flow of the reaction mixture having the desired arrangement in the reaction module in the direction of the cooling zone. For example, in the middle of the reaction module, in a single stream spaced from the walls of the module body.
  • the reaction mixture cooling zones 4-1 and 4-2 are adapted to supply refrigerant to the internal cavity of the module, for example, using a refrigerant refrigerant supply system configured to control refrigerant flow parameters, for example, refrigerant volume and flow rate, and flow configuration.
  • a refrigerant stream can be formed in the form of a hollow cylinder having 5-1 and 5-2 around the reaction mixture in the area of the reaction zone a refrigerant layer sufficient to ensure that the temperature of the reaction mixture in the reaction zone is not higher than 600 0 C.
  • the supply of refrigerant is carried out in the direction of flow of the reaction mixture with the formation of a refrigerant stream having a space inside the stream to accommodate the flow in it the reaction mixture is completely along the entire length of the stream or part thereof.
  • This can be achieved, for example, by performing devices 13-1, 13-2 and 13-3 of the supply of refrigerant, for example, collector type, having slit-like outlet openings located near the inner surface of the reactor vessel 1 or in the plane of the cross section of the vessel at the inlets in zones 4-1 and 4-2 of cooling.
  • the devices 13-1, 13-2 and 13-3 of the refrigerant supply can be made with the possibility of regulating the thickness of the refrigerant layer around the flow of the reaction mixture, for example, by changing the angle of inclination and the orifice of the slits.
  • the refrigerant supply devices 13-1 and 13-2 can be configured to provide a refrigerant stream having a space inside to accommodate the entire stream of the reaction mixture or part thereof and having a different thickness of the refrigerant layer, for example, device 13 -1 and 13-2 of the refrigerant supply can be made multi-tiered and multi-level, placed, for example, in various cross sections of the reaction modules 2-1 and 2-2.
  • a cold hydrocarbon-containing feed gas or a cooled hydrocarbon-containing exhaust gas or an aqueous solution of organic by-products formed after methanol evolution, or a gas-vapor mixture with a hydrocarbon-containing or cooled hydrocarbon-containing exhaust gas, which can be delivered to devices 13-, can be used.
  • 1, 13-2 and 13-3 of the refrigerant supply to the cooling zones 4-1 and 4-2 can be carried out through pipelines.
  • reaction zones 5-1 and 5-2 are equipped with devices 14-1, 14-2 and 14-3 for measuring temperature inside the zones and at the boundaries with cooling zones 4-1 and 4-2.
  • the methanol production device may also contain at least one more heat exchanger 15 for cooling the products leaving the heat exchanger 9 and other devices connected by a piping system to provide cooling and separation of the products into components to be separated or recycled.
  • a separator 16 - separation of gaseous and liquid products using a column 17 - separation of methanol in the collector 18 from an aqueous solution of organic by-products sent to the collection tank 20.
  • gaseous products from the separator 16 using the compressor 19 can be fed into the mixer 22, and water the solution from the collection tank 20 with the help of the pump 21 can also be supplied to the mixer 22, and then the mixture of gaseous products with the aqueous solution can be used as a refrigerant in the cooling zones 4-1 and 4-2.
  • the method for producing methanol was carried out in plants according to the invention using one reactor 1, including two cylindrical reactor modules 2-1 and 2-2, in which the mixing zones 3-1 and 3 were respectively formed: -2, cooling zones 4-1 and 4-2 and reaction zones 5-1 and 5-2.
  • the reactor module 2-1 in which the mixing zones 3-1 and 3 were respectively formed: -2, cooling zones 4-1 and 4-2 and reaction zones 5-1 and 5-2.
  • the reactor module 2-1 in which the reactor module 2-1:
  • the mixing zone 3-1 was made in the form of a multi-flow mixer of the “tube-in-tube” type, and due to intensive turbulization of the incoming flows of the initial gaseous products, their rapid mixing was ensured with the formation of a stream of a homogeneous reaction mixture;
  • the formation of the cooling zone 4-1 was carried out by supplying a flow of refrigerant through a multi-threaded device located around the circumference of the reactor module 2-1, forming a flow of refrigerant in the form of a hollow cylinder.
  • - cooling zone 4-2 was formed by supplying refrigerant through two multi-threaded devices similar to a multi-threaded device installed in the cooling zone 4-1 of the reactor module 2-1. Moreover, these multi-threaded refrigerant supply devices were placed at a distance of 1/3 and 2/3 of the length of the reactor module 2-2 from the mixing zone 3-2.
  • example 1 used a vapor-gas mixture of an aqueous solution of organic by-products formed after the separation of methanol in column 17, and said vapor-gas mixture from a collection vessel 20 was supplied to cooling zones 4-1 and 4-2 with a stream of an initial cold hydrocarbon-containing gas;
  • a similar vapor-gas mixture from a collection tank 20 was fed into cooling zones 4-1 and 4-2 with a stream of cooled off-gas-containing off-gas.
  • example 2 the execution of the installation according to the invention was a recirculation scheme.
  • hydrocarbon-containing gas was piped 6 from a gas source through a compressor 7 to a manifold 8, for example, a piping for gas distribution.
  • the main stream of the hydrocarbon-containing gas was supplied to the heat exchanger 9 for heating the gases leaving the reactor 1.
  • the auxiliary stream of the hydrocarbon-containing gas from the manifold 8 was supplied to the mixer 22 to form a refrigerant stream.
  • Pipeline 10 indicated the main stream — heated hydrocarbon-containing gas — into the reactor module l.
  • Compressed oxygen-containing gas was also supplied to the reactor modules 2-1 and 2-2 from compressor 11 via pipelines 12-1 and 12-2.
  • the heated hydrocarbon-containing gas was mixed with compressed oxygen-containing gas.
  • reaction zone 5-1 part of the hydrocarbon-containing gas was oxidized with oxygen, which caused the mixture to heat up, but the temperature in the oxidation zone was maintained in the required range of 520-570 0 C according to the invention by cooling the reaction mixture with a coolant stream supplied through the device 13-1 to zone 4-1 of cooling.
  • the flow rate of the refrigerant was controlled using device 14-1.
  • a mixture of products of the oxidation process and feed gases from reactor 1 was fed into a heat exchanger 9, where the feed stream of a hydrocarbon-containing gas was heated.
  • the final cooling of the stream, if necessary, was carried out in the heat exchanger 15.
  • the stream was fed to a separator 16, in which liquid products, including organic by-products, were separated.
  • RU, 2162460, Cl an analogue characterizing the prior art of the present invention
  • the initial hydrocarbon-containing gas was a mixture of the following composition,% by volume: methane - 98, carbon dioxide - 1 and nitrogen - 1.
  • the temperatures of the initial hydrocarbon-containing and oxygen-containing gases at the inlet of the methanol production unit were about 20 C.
  • Example 1 all exhaust gas from the separator 16 was sent for disposal, and in Example 2, the exhaust gases from the separator 16 were partially supplied for disposal. In this case, gases partially pressurized by the compressor 19 were supplied to the mixer 22 to form a refrigerant stream ..
  • Example 1 liquid products from the separator 16 were fed to a distillation column 17 to isolate the target product, methanol, from the mixture, which was then taken to methanol collector 18.
  • An aqueous solution of organic by-products was collected in a collection tank 20 and then pumped 21 to a mixer 22 to form a refrigerant stream.
  • the main process parameters are presented in the table.
  • the table shows that, compared with the known production method according to example 3, in the methanol production methods presented in examples 1 and 2, the working pressure in the reactor is lower and is 7.5 MPa, the temperature at the inlet to the reactor is increased and is 450 0 C, and due to the partial disposal of secondary of products, the methanol yield is higher than in example 3, and is 654 kg / hour (example 1) and 808 kg / hour (example 2).
  • the methanol production method according to the invention can be carried out in a plant for its implementation according to the invention using known technologies, known structural materials and equipment.
  • the plant for producing methanol according to the invention can be used in complexes of traditional methanol production with modification of process piping and equipment used in the reactor unit.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne la chimie organique et notamment un procédé de fabrication de méthanol par l'oxydation d'un gaz hydrocarboné. Le procédé se distingue en ce que l'on forme dans un module de réacteur (1) une zone de refroidissement (4-1), (4-2) un mélange de réaction par l'injection continue d'un agent caloporteur dans le sens de déplacement du flux de mélange de réaction après la sortie du mélange de réaction de la zone de mélangeage (3-1), (3-2). On forme un flux de caloporteur comportant à l'intérieur un espace pour accueillir au moins une partie de la zone de réaction (5-1), (5-2) et l'on maintient dans cette partie de la zone de réaction (5-1), (5-2) à l'intérieur du flux de caloporteur une température du mélange réactionnel de 520-600°, ce qui permet d'augmenter la sortie de produit fini et de réduire la formation de produits secondaires. La zone de refroidissement (4-1), (4-2) est réalisée de manière à permettre de varier le débit de caloporteur pour assurer la température nécessaire du mélange de réaction à l'intérieur du flux de caloporteur.
PCT/RU2007/000070 2007-02-14 2007-02-14 Procédé de fabrication de méthanol et installation correspondante WO2008100170A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/RU2007/000070 WO2008100170A1 (fr) 2007-02-14 2007-02-14 Procédé de fabrication de méthanol et installation correspondante

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Application Number Priority Date Filing Date Title
PCT/RU2007/000070 WO2008100170A1 (fr) 2007-02-14 2007-02-14 Procédé de fabrication de méthanol et installation correspondante

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WO2008100170A1 true WO2008100170A1 (fr) 2008-08-21

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4618732A (en) * 1985-05-20 1986-10-21 Gesser Hyman D Direct conversion of natural gas to methanol by controlled oxidation
RU2162460C1 (ru) * 2000-06-06 2001-01-27 Арутюнов Владимир Сергеевич Способ производства метанола и установка для производства метанола
RU2203261C1 (ru) * 2002-03-15 2003-04-27 Открытое акционерное общество "Метокс Интернейшнл" Способ получения метанола и установка для его осуществления

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4618732A (en) * 1985-05-20 1986-10-21 Gesser Hyman D Direct conversion of natural gas to methanol by controlled oxidation
RU2162460C1 (ru) * 2000-06-06 2001-01-27 Арутюнов Владимир Сергеевич Способ производства метанола и установка для производства метанола
RU2203261C1 (ru) * 2002-03-15 2003-04-27 Открытое акционерное общество "Метокс Интернейшнл" Способ получения метанола и установка для его осуществления

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