A method of producing methanol and installation for its implementation

 

The invention relates to an improved process for the preparation of methanol by direct oxidation of hydrocarbon gas, comprising the sequential feeding site mixing of the reactor, which is located in the upper part of the reactor, the heated hydrocarbon gas and compressed air, followed by direct oxidation of the hydrocarbon gas, cooling the reaction mixture and separation, in which the cooled reaction mixture is separated into exhaust gases and liquid products, and regeneration obtained in the process of separation of methanol, with the release of methanol and exhaust gas discharge, and the oxidation of the hydrocarbon gas is carried out in two stages: homogeneous oxidation of the tubular part of the reactor and subsequent heterogeneous oxidation in the shell side of the reactor using a two-layer catalyst at a temperature 390-4900C and a pressure of 8.0 MPa, and cooling the reaction mixture is performed first in the heat exchanger “gas-gas”, then in the air cooler gas. The invention also relates to an apparatus for the production of methanol containing a source of hydrocarbon gas, the reactor for the oxidation of methane with a node in the mixture of compressed air and the heated methane before the reaction in the exhaust gases and methanol raw the regeneration unit of crude methanol, and the source of the hydrocarbon gas is on the installation of complex gas, the reactor consists of two reaction zones, one of which is a reaction zone for homogeneous oxidation and the other zone is a zone for heterogeneous oxidation using a two-layer catalyst, and the first layer is a metal-containing catalyst for improving the selectivity, and the second layer consists of oxides of Mg, Zn, Ba, Zr for the oxidation of formaldehyde specified homogeneous reaction occurs in the tubes of the reactor, and in the shell side of the reactor, filled with two-layer catalyst is heterogeneous oxidation of methane to methanol, when this reactor is equipped with a multichannel thermocouple, a cooling device in the form of a heat exchanger installed in series “gas-gas” and an air cooler connected to the reactor, the installation of complex gas separator connected to the regeneration unit of crude methanol. Energy-saving method allows to simplify the technology, to reduce the number of pieces of equipment. 2 AD. and 1 C.p. f-crystals, 1 tab., 2 Il.

The present invention wordstream gas (natural gas).

Natural gas is projected to be a major hydrocarbon resource for energy and chemical industry of the XXI century. The main deposits of gas and gas condensate are located in remote areas of the Far North. The sharp decline in gas production in the Russian Federation due to the fact that large deposits, such as Urengoy, Yamburg, a bear entered a period of declining production. Replenishment of production associated with the development of small energy and the shelf of the Northern seas, which will be hampered by the lack of transport schemes and inhibitors. The main inhibitor to combat hydroabrasive in gas production is methanol, the delivery of which to the remote fields represents a huge cost several times the price to buy methanol from petrochemical plants.

The creation of small units of production of methanol by the method of converting natural gas directly from fields in the installations of complex gas treatment plants would solve the problems described above for the gas industry. Considering the fact that a further increase in gas production will be done at the expense of numerous small fields, conversion of methane to methanol. The wide industrial application has a steam conversion of methane into synthesis gas (mixture of CO and H2with its subsequent catalytic conversion to methanol (Karavaev M. M., Leonov, C. E. and other Technology of synthetic methanol. - M.: Chemistry, 1984, S. 72-125). However, implementation of this process requires complex equipment, high demands on the purity of the gas, and the high cost of energy for the production of synthesis gas and its treatment, a large number of intermediate stages of the process, the lack of profitability of small and medium enterprises with a capacity of less than 1000 tons/day.

A known method of producing methanol, comprising separate feeding pre-heated to 200-500°C hydrocarbon gas under pressure from 2.5 to 15 MPa and an oxygen-containing gas in the mixing chamber, the subsequent stage partial oxidation of methane with oxygen concentrations of 1-4% vol. with the addition of reagents (metal oxide catalyst, the higher gaseous hydrocarbons or oxygen-containing compounds, cold oxidant in the reaction zone of the reactor, cooling the reaction mixture in the heat exchanger, separation of methanol from the liquid reaction products in the separator, the flow of exhaust gaseous reaction products at the reactor inlet (EN 2049086 AND the common gases leads to reduction of the yield of methanol and increase the likelihood of sooting.

A method of producing methanol, comprising separate feeding into the mixer hydrocarbon gas (natural gas or methane) and oxygen-containing gas (air or oxygen), the subsequent filing of the mixture in an inert reactor, gas-phase partial oxidation of hydrocarbon gas in the reactor under a pressure of 1-10 MPa for 2-1000 seconds at a temperature of 300-500°C in the absence of catalyst, the oxygen content of 2-20 vol.%, the allocation of methanol in the condenser of the reaction products, the return exhaust the reaction gas containing unreacted methane, in the mixture with a source of hydrocarbon gas in the first reactor or the second reactor serially connected to the first reactor (GB 2196335). The method provides a high yield of methanol, and 5-15% methane can react with each pass through the reactor, however, a high response time limits the performance of the reactor methanol.

A known method of producing methanol by separate feed and oxidation of hydrocarbon gas to oxygen-containing gas at 370-450°C., a pressure of 5-20 MPa and time contact them in the reactor of 0.2-0.22 seconds, cooling the reaction mixture warmed up to 330 to 340°With the introduction into the reactor metapontum heat exchangers, installed in the reactor, after which the reaction mixture flows on 2-3 consecutive stages of oxidation (SU 1336471 A1). In the first case, the need for additional flow and re-allocation of methanol leads to its inevitable losses that otherwise require the installation of additional cooling circuits of circulation in additional cooling agent.

The closest technical solution is a method for the production of methanol (EN 2162460 A), including separate feeding successively compressed and heated hydrocarbon gas and compressed oxygen-containing gas into the mixing zone of consecutive reactors, followed by gas-phase oxidation of a hydrocarbon gas at initial temperature up to 500°C, pressure up to 10 MPa and the oxygen content of not more than 8 vol.%, cooling the reaction mixture after each reaction zone of the reactor at 70-150°C through the wall of the flow of cold hydrocarbon gas, quenching of the reaction mixture after the last reaction zone by lowering the temperature of the reaction mixture not less than 200°C. for a time which is less than 0,1 time of her stay in the reaction zone, cooling and separation of chilled reaction ctor, rectification of liquid products with the release of methanol, the flow of exhaust gases in hydrocarbon source gas, or burning.

The known method does not provide the required heat removal rate of the reaction that leads to the necessity of reducing the degree of conversion of the hydrocarbon gas. In addition, even using as oxidant oxygen is not possible to effectively recycle hydrocarbon gas due to the rapid increase in the concentration of carbon oxides. A considerable part of the supplied oxygen is consumed for oxidation of CO in the CO2, leading to additional reduction in the degree of conversion of the carbon source gas and further overheating of the reaction mixture. In addition, the additional amount of hydrocarbon source gas must be burned to provide steam stage distillation of liquid products.

Known plant for production of methanol containing successively installed and connected by pipelines mixing chamber connected to separate sources of hydrocarbon gas and air or oxygen, the reactor from an inert material with heating elements for incomplete Oia methanol from the reaction products, capacity for recycled gaseous reaction products by pipeline to serve them in the original hydrocarbon gas or mixing chamber (GB 2196335). However, a high residence time of the reactants in the reactor does not provide high performance installation, which makes the process unsuitable for industrial use.

A known device for producing methanol, which contains the hydrocarbon source gas, the compressor and the heater to compress and heat the gas, the source of oxygen-containing gas with a compressor, successively installed reactors with sequential mixing and reaction zones with the supply pipe hydrocarbon gas in the first mixing zone of the reactor and the oxygen-containing gas into each of the mixing zone, recuperative heat exchangers for cooling the reaction mixture through the wall of the flow of cold hydrocarbon gas, installed near the output ends of all of the reaction zones of the reactor pipelines for further supplying heated hydrocarbon gas in a heater, a cooler-condenser, a separator for separating the exhaust gases and liquid products from gas, and a pipeline for supplying the waste liquid oxygenated products in the first mixing zone of the reactor (EN 2162460 A).

The impossibility of rapid heat removal vysokomaslichnoy volume of the oxidation reaction of hydrocarbon gas leads to the need to reduce the amount of hydrocarbon gas and, consequently, the degree of conversion of the hydrocarbon gas. In addition, even when used as an oxidizer oxygen impossible effective recycling of hydrocarbon gas due to the rapid increase in the concentration of carbon oxides. A considerable part of the supplied oxygen is consumed for oxidation of co and CO2, leading to additional reduction in the degree of conversion of the hydrocarbon source gas and further overheating of the reaction mixture. The installation also requires the burning of additional quantities of hydrocarbon source gas to provide steam stage distillation of liquid products. The necessity of cooling gas-liquid mixture after each reactor for the separation of liquid products and its subsequent heating before the next reactor leads to considerable complication of the technological scheme, the HC method of producing methanol, including consistent flow at the site of mixing, located in the upper zone of the reactor, compressed air and heated to 390°C hydrocarbon gas with a pressure of 8.0 MPa, the acceleration of the beginning of the reaction, 0.5 sec, homogeneous reaction occurs in the tubular part of the reactor, the heterogeneous reaction occurs in 2-layer catalyst located in the shell side of the reactor, cooling the reaction mixture occurs in the regenerative heat exchanger “gas-gas”, the final cooling of the reaction mixture before separation occurs in the air cooler (air cooler) gas separation process liquid products with the release of methanol and the flue gas, according to the invention for the installation of complex gas.

The required inlet temperature in the reactor is achieved by heating the gas to a temperature of 390°C in a tubular furnace, the initial oxygen concentration before the reaction zones to 2.0% by adding compressed air to the node in the mixing reactor.

The problem is solved also by the fact that on an installation for the production of methanol containing a source of hydrocarbon gas with the installation of complex gas reactor for oxidation of hydrocarbon gas consisting of zones MVS shell side of the reactor, the objective of the first catalyst layer - improving the selectivity of the oxidation of methane to methanol on metal-containing catalysts Ni, Co, Fe, the task of the second catalyst layer - destruction of formaldehyde are more mild oxidizing agents, such as oxides of SB, Zn, Ba, Zr.

The problem is solved by the fact that it is experimental-industrial plant in connection with the frequent contradictions in the literature data on the composition of the catalyst, the solution is achieved through experimental testing of catalysts, the design of the reactor allows you to try a wide range of catalysts.

Thus, in the method of producing methanol hydrocarbon gas with the installation of complex gas is exposed to direct oxidation reactor which is supplied with compressed air, and the reaction is carried out in two stages at a temperature 390-490°C With 1% conversion temperature rises to 47°C, and cooling the reaction mixture in the reactor directly at oxygen concentrations up to 2% will not be required as methanol to 500°C and remains stable until the final hardening of about 4, which determines the distance from the reactor to the heat exchanger-recuperator heat.

The presence of peregorodki occurs in the heat exchanger “gas-gas”, where in the annulus as a cooling agent is supplied a source of hydrocarbon gas with a temperature of 20°C and a pressure of 8.0 MPa, then the reaction mixture is supplied to the air cooler gas. The cooled reaction mixture to 15-25°C enters the separator, which is allocated a dry gas and methanol raw.

Methanol raw with a concentration of up to 50% is directed to the regeneration unit of methanol, where are trademark methanol 95% concentration, and the VAT residue containing a small amount of formaldehyde, is directed to the horizontal a flare for burning.

The main difference method and installation for the production of methanol is the method of successive direct oxidation of methane to methanol in a reactor by two methods: homogeneous oxidation in the tubular part and catalytic oxidation in the annular space with the following parameters: temperature 390-490°C, pressure of 8.0 MPa, the time of reaction is about 2.5 s, the oxygen concentration to 2%. To stop the oxidation of methanol using tubular stainless steel grille as partitions, which also serves to secure the tubes of the reactor and to separate the tubular portion and the annulus of Rean conversion of hydrocarbon gas per reactor. This, in turn, increases the yield of methanol. The application of this method greatly reduces the amount of equipment and, in turn, facilitates the process control reactions, its automation and reduces the cost of the project to install, increases the profitability of the process. The application of this method of production of methanol is facilitated by the fact that in terms of gas and gas condensate fields allows to obtain methanol in a relatively straightforward manner, which, in turn, reduces the requirements to the qualification of the staff to the level of the operators on the production of gas and condensate. The advantage of this method is that the exhaust gases are returned back to the process plant of complex gas treatment, without affecting the mode of its operation and quality of marketable gas, as the capacity of the plant for production of methanol is much less than the capacity of the complex gas treatment, for example at the output of unit 10 billion m3gas/year increase in the content of nitrogen compounds in the product gas will be less than 0.37% of the performance of the unit to produce methanol 6 thousand tons/year, which corresponds to the requirements of the Coolant installation on gas installations, where the content of2+C3in the source gas for up to 7 vol.%, that, in turn, increases the yield of methanol.

This unit is the production of methanol is different in a way that is environmentally friendly production, where there are no harmful emissions.

Further, the invention is illustrated with specific examples of its implementation and the accompanying drawings, on which:

Fig.1 depicts a General view of the installation for the production of methanol;

Fig.2 depicts a scheme of the reactor.

Device for producing methanol includes a reactor 1 (Fig.1) for the oxidation of methane directly into the methanol. The reactor 1 consists of two zones 2 and 3, one of which, zone 2, designed for homogeneous gas-phase reactions, provided with a device 4 for mixing compressed air and methane and the device 5 of the tubular part, where the tubing passes homogeneous reaction, and zone 3 is an annular space is filled with 2-layer catalyst, where there is a heterogeneous reaction. The tube is mounted in tube sheets, which are partition for distribution and contribute to the hardening of methanol. In addition, the reactor 1 is equipped with multi-channel thermionic mixture, which is made in the form of a heat exchanger “gas-gas” 8 and an air cooler the air cooler gas 9 connected to the reactor 1. The heat exchanger “gas-gas” 8 communicated with the installation of complex gas 10 and the furnace 11. The cooled reaction mixture is supplied to the separator 12, which is connected to the gas treatment unit 10 and unit methanol regeneration 13. The reactor 1 is connected to the compressor 14 for compressed air and oven 11 heated hydrocarbon gas.

Hydrocarbon natural gas (methane 92-98%) installing the drying gas passes through the heat exchanger “gas-gas” 8 (Fig.1) with a temperature of 10-20°C, where the cooling of the reaction mixture, and, negresses to a temperature of 300-350°C, through the furnace heating 11 with temperature 390-400°C arrives at the site of mixing 4 of the reactor 1, which is supplied compressed air with a temperature of 50°C and a pressure of 8.0 MPa with an air compressor 14 in a ratio of up to 2% vol. the oxygen.

In the reaction zones 2 and 3, the oxidation of methane to methanol, and the reaction mixture temperature up to 500°C enters the tube of the heat exchanger “gas-gas” 8 and heating the source gas to 350°C, are directed to the office of air cooling gas 9, thence with a temperature of 20-25°C post is rotatin in the gas treatment unit 10, and methanol raw block methanol regeneration 13. Block methanol regeneration 13 commodity methanol 95% concentration goes to the Park methanol and VAT residue from the regeneration unit of methanol 13 is directed to the horizontal flare device installation complex gas 10 for combustion.

Example, confirming the ability of the proposed method for the production of methanol.

Cold dry natural gas (methanol content 98%) from the unit 10 with a flow rate of 42940 kg/h with pressure P=8.0 MPa through the heat exchanger “gas-gas” 8, where it is heated to 350°C, is directed through the furnace heating 11 with temperature 390-400°C in the reactor 1 which is supplied with compressed air in an amount 7400 kg/h from the compressor 14. The reaction takes place in reactor 1 in the reaction zones 2 and 3. The reaction time up to 2.5 C. Then the reaction mixture through the heat exchanger “gas-gas” 8 and air cooler 9 is fed into the separator 12. Dry gas from the separator in the number 48350 kg/h is returned to the system 10, and methanol raw number of 1850 kg/h goes to block methanol regeneration 13.

Claims

1. A method of producing methanol, comprising the sequential flow is atogo air, subsequent direct oxidation of hydrocarbon gas, cooling the reaction mixture and separation, in which the cooled reaction mixture is separated into exhaust gases and liquid products, and regeneration obtained in the process of separation of methanol, with the release of methanol and exhaust gas discharge, characterized in that the oxidation of the hydrocarbon gas is carried out in two stages: homogeneous oxidation in the tubular part of the reactor and subsequent heterogeneous oxidation in the shell side of the reactor using a two-layer catalyst at a temperature 390-490C and a pressure of 8.0 MPa, and cooling the reaction mixture is performed first in the heat exchanger gas - gas, then air cooler gas.

2. The method according to p. 1, characterized in that the reaction zones support the oxygen concentration to 2%, the acceleration of the beginning of the reaction, 0.5 sec, a reaction time of 2.5 s, the maximum temperature at the end of the reaction is not more than 490C, which is lower than the temperature oxidation of methanol, which allows not to remove heat from the reaction zone.

3. Installation for the production of methanol containing a source of hydrocarbon gas, the reactor for the oxidation of methane to host the mixture is aracia, a separator for separating the reaction products in the exhaust gases and methanol, raw, block regeneration methanol, characterized in that the hydrocarbon source gas is on the installation of complex gas, the reactor consists of two reaction zones, one of which is a reaction zone for homogeneous oxidation and the other zone is a zone for heterogeneous oxidation using a two-layer catalyst, and the first layer is a metal-containing catalyst for improving the selectivity, and the second layer consists of oxides of Mg, Zn, Ba, Zr for the oxidation of formaldehyde specified homogeneous reaction occurs in the tubes of the reactor, and in the shell side of the reactor, filled with two-layer catalyst is heterogeneous oxidation of methane to methanol, the reactor is equipped with a multichannel thermocouple, a cooling device in the form of sequentially installed heat exchanger gas - gas and air cooler connected to the reactor, the installation of complex gas separator connected to the regeneration unit of crude methanol.

 

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