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INVENTION
Patent of the Russian Federation RU2062143
INSTALLATION FOR METHANOL PRODUCTION
The name of the inventor: Tikhomirov AG; Klimentyeva G.V .; Kustov L.Ya. .; Nesterov GI; Matveyev IK; VM Timokhin; Zhukov AA; Zhukov A.A.
The name of the patent holder: Specialized design and technological bureau of the Territorial Production Specialized Transport Association "Spetstrans"
Address for correspondence:
Date of commencement of the patent: 1993.07.12
The invention relates to the field of organic chemistry, in particular to installations for the production of methanol. The methanol production plant includes a turbocharger communicated with a methanol conduit, an oxygen supercharger communicated with an oxygen pipeline, a gas heater, a reactor, a condensing condenser, a control station, a power source connected via a rectifier to a control station and a voltage regulator, Rotary dampers installed on process pipelines, and electrical connections to control plant elements.
DESCRIPTION OF THE INVENTION
The invention relates to the field of organic chemistry, in particular to installations for the production of methanol.
An installation for the industrial synthesis of methanol is known (see LA Tsvetkov's textbook "Organic Chemistry", M. "Enlightenment", 1988, pp. 108-111).
The plant for industrial methanol synthesis comprises a turbocompressor connected by a process pipeline with a synthesis gas source, a heat exchanger, a synthesis column, a condensing condenser, a separator and a methanol collector connected to each other by process pipelines.
The essence of methanol synthesis lies in the fact that the synthesis gas is compressed by a turbocharger, mixed with unreacted gas and sent to a heat exchanger, where the gas mixture is heated to a predetermined temperature by waste gases. Then the mixture of gases enters the synthesis column, where the target process is carried out. The reaction products coming out of the synthesis column enter the heat exchanger, where they heat the gas mixture going to synthesis, then pass through the condenser condenser and then proceed to the separator. In the separator, alcohol is separated from unreacted gases, which are returned to the process by a circulating compressor.
The technological process takes place at a temperature of 250-300 ° C , pressure 10 MPa with the use of catalysts of oxides of zinc, chromium, copper.
The described scheme of obtaining methanol through synthesis gas has drawbacks . At the current scale of its production of 20 million tons per year, it is advisable to use the process, however, when methanol is introduced as a mass automobile fuel, global methanol production problems arise because of the high cost of the process and material costs.
Currently, 75% of the total cost of methanol produced accounts for the synthesis gas itself, and 70% of all capital expenditures and a huge amount of energy. It follows from the calculations that any production with a capacity of less than 1 million tons per year is unprofitable. It follows that these industries have large initial costs and long payback periods. A plant for the production of methanol is known, based on the method of direct homogeneous oxidation of methane ( see the article by VS Arutyunov, VIVedeneev and N.Yu. Krymov., "From methane methanol", "Chemistry and life", 1992, N 7, pp . 35-38 ).
The essence of the process for the production of methanol by direct homogeneous oxidation of methanol is that methane and oxygen under a pressure of 75-100 atm are heated in the range of 350-400 ° C and are fed to a straight through tube reactor, followed by circulation of the reaction mixture.
The methanol production plant based on this method comprises methane and oxygen supply pipelines, respectively, by a turbocharger and a supercharger through a gas preheater to a reactor in the form of a co-current pipe and connected to a condenser condenser, the latter being provided with an additional process pipeline with a turbocharger inlet and Control station.
A disadvantage of the known plant for the production of methanol is a relatively low productivity, since in a single cycle only a small fraction of methane is converted to methanol at about 3%
It is known that a mixture of methane with oxygen or air during ignition can explode. The strongest explosion is obtained if methane is mixed with oxygen in a volume ratio of 1: 2. The optical ratio of the volume in the explosion of methane with air is 1:10 .
Based on the foregoing, the known plant for the production of methanol is not safe.
The closest technical solution to the claimed plant is an installation for the production of methanol, indicated in the article by VS Arutyunova, V.I. Vedeneeva and N. Yu. Krylov. "From methane-methanol" (see the journal Chemistry and Life, 1992, N 7, pp.35-38) .
The purpose of the invention is to increase the productivity and safety of the installation.
To achieve the object of the invention, a known methanol production plant comprising methane and oxygen supply pipelines, respectively, by a turbocharger and a supercharger through a gas preheater to a reactor configured as a co-current pipe and connected to a condenser condenser, the latter being provided with an additional process line with a turbocharger inlet, And the control station is provided with ejecting devices, a casing covering the middle part of the rectilinear reactor tube and a check valve installed in the additional process pipeline, the gas heater is made in the form of a cylindrical heat-insulated outer shell in which a straight-through heat-conducting pipe is mounted, The outlet of the turbocompressor and the other end to the inlet of the rectilinear reactor tube, a sectional thermal electric heater electrically connected via a voltage regulator to a power supply and mounted in a heat conducting body in contact with the direct flow heat pipe and a thermal conductive oxygen converter communicating with its inlet to the oxygen blower outlet , And an outlet with an additional reactor inlet located at the other end of the downstream pipe, wherein the portion of the middle portion of the rectilinear reactor tube is perforated and together with the casing is made in the form of an annular sealed cavity communicated by conduits with a condenser condenser, Ejection devices.
In addition, in order to achieve the object of the invention, the heat-conducting oxygen converter is made in the form of two hollow rings, one of which is communicated with the discharge of the oxygen supercharger and the other with an additional reactor inlet, the rings communicating with each other by straight-through pipes surrounding the electric heater; The portion of the middle part of the rectilinear reactor tube is provided with at least two grids arranged opposite the ejection device outlets and made of a platinum alloy; The gas heater is provided with heat conducting plates contacting the electric heater body and the straight tubes of the thermal conductive oxygen converter.
In the case of patent studies, the claimed totality of characteristics of the methanol production unit was not found to achieve the objective of the invention. From the analysis of the set of essential features of the installation, it follows that the proposed new gas heater and reactor, in the presence of new technological connections, ensure an increase in the productivity and safety of the installation.
The increase in plant productivity is achieved due to counterpropagating flows of methane and oxygen, which ensure intensification of the interaction of gases formed and accelerated by ejecting devices, while ejecting devices exclude the formation of stagnant zones in the front and rear parts of the reactor, which increases the safety of the installation.
Specialists of the Institute of Chemical Physics . NN Semenova found that the rate of methanol formation during the oxidation of methane, as well as other ongoing reactions in the reactor, increases as the content in the mixture of one of the initial oxygen gases decreases, which increases the efficiency of the process by almost 20%. The proposed installation is pressurized In 7.5 10 MPa , the gas medium consisting predominantly of methane and oxygen is regulated in the reactor by means of a gas ratio regulator in the volume ratio methane: oxygen equal to (0.7-2.1): 1 . With this gas ratio, the conditions for the explosion do not arise when they leak from the units of the installation.
Thus, the totality of features ensures the achievement of the objective of the invention.
In the applicant's opinion, the technical solution is new, as it is not known from the state of the art. The technical solution has an inventive level, as for a specialist, it does not explicitly follow from the state of the art in this field. The technical solution is industrially applicable in view of the fact that the signs can be industrially mastered at chemical industry enterprises.
FIG. 1 schematically shows a plant for the production of methanol
With control block diagram, general view
FIG. 2 the same, longitudinal section of the gas heater, on an enlarged scale
FIG. 3 is the same, the cut along AA in FIG. 2
FIG. 4 the same, longitudinal section of the reactor, on an enlarged scale
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FIG. 5, the same as the node B in FIG. 4; In Fig. 6 the same, the longitudinal section of the condenser-condenser
The methanol production unit includes a turbocharger 1 communicated with a methane (natural gas) line 2, an oxygen supercharger 3 communicating with an oxygen conduit 4, a gas preheater 5, a reactor 6, a condenser condenser 7, a control station 8, a power supply 9, Connected via a rectifier 10 to a control station 8 and a voltage regulator 11, drive valves, rotary flaps mounted on process pipelines, and electrical connections for controlling the elements of the plant.
A turbocompressor 1 of known design using methane or natural gas as an energy source through conduit 12 and drive valves 13, 14 into its combustion chamber 15 provides methane feed at a pressure of 7.5 10 MPa through conduit 16 with a drive rotary damper 17 to Inlet 18 preheater 5 gases.
The oxygen compressor 3 of a known design, for example a piston type, is driven by a DC electric motor 19 and supplies oxygen at a pressure of 7.5 10 MPa through conduits 20, 21 with a drive valve 22 and a rotatable shutter 23 into a gas preheater 5. The gas preheater 5 is a cylindrical body 24 with lids 25, 26 sealed from the ends of the casing 24, the casing and covers being thermally insulated from the outside. A direct-flow heat-conducting pipe 27 for heating methane installed in the covers 25, 26 and a partition 28 with openings 29, 30, 31, a sectioned thermal electric heater 32 and a thermal-conducting oxygen converter 33 are mounted in the housing 24. The housing 24 can be installed both horizontally and vertically.
The direct-current heat-conducting pipe 27 is connected to its input gate 17 with a drive rotary damper 17 for regulating a predetermined volume of methane, and its outlet 34 is connected via a line 35 to the inlet 36 of the reactor 6. The sectional thermal electric heater 32 is at least two cylindrical bodies 37 , 38, in the cavities of which the heater sections 39, 40 are mounted for different capacities. The internal surfaces of the housings 37, 38 are made contacting with a straight-through heat-conducting pipe 27. Each section 39, 40 is made of a refractory and heat-resistant material with a high specific resistance with a maximum heating area. The heating elements are electrically insulated from each other by means of electrical insulators 41 to prevent their destruction. Electrical insulators 41 are made of ceramics. Each section 39, 40 of the electric heater 32 is connected to a voltage regulator 11 of a known design by means of electrical connection elements 42, 43 (the electrical connection elements of section 39 are not shown conditionally). The voltage regulator 11 is electrically connected to the power supply 9.
The power supply source 9 is an alternating current generator whose shaft is connected to the turbocharger 1. In another modification of the embodiment of the power supply 9, the source 9 can be implemented as an alternating current network of the enterprise.
The thermal-conducting oxygen converter 33 can be made in the form of two hollow-ring rings 44, 45 of a rectangular cross-section, one of the rings 44 is communicated with the outlet 46 of the oxygen blower 3 (the inlet port of the converter 33 is not shown conditionally), and the other ring 45 by means of a branch pipe 47 and a conduit 48 With the additional input 49 of the reactor 6, the rings 44, 45 being connected to each other by straight-through pipes 50 passed through the openings 30 of the partition 28. The pipes 50 encircle the sectional thermal electric heater 32. A plurality of heat-conducting plates 51 connecting the cylindrical bodies 37, 38 to the tubes 50 of the thermal-conductive oxygen converter 33. This provides heat transfer for oxygen heating.
The reactor 6 is made in the form of a straight-through pipe 52, insulated from the external environment (the thermal insulation is not shown conditionally). The diameter and length of the tube 52 of the reactor 6 is determined depending on its design capacity. The ends of the pipe 52 are hermetically sealed with covers 53 and 54 with central holes representing the inputs 36, 49 of the reactor 6. The lines 36, 49 are tightly connected to the conduits 35, 48 by means of flange connections 55, 56. In the cavities of the covers 53, 54 made in In the form of hemispheres, ejecting devices 57, 58 for accelerating methane and oxygen gas flows are mounted, as well as for sucking gases from the near-wall zones through annular gaps 59 formed between the first stage nozzles 60 and the second stage nozzles 61. Such a design ensures intensive interaction and mixing of gases. The portion of the middle portion of the coiled tubing 52 is perforated and is enclosed by a casing 62 which is sealed to the pipe 52 and forms an annular sealed cavity 63 communicating through the conduits 64, 65, 66 and the drive valves 67, 68 with the condenser 7. The apertures 69 of the perforated portion The middle part of the pipe 52 is selected with a minimum hydraulic resistance.
The portion of the middle portion of the coiled tubing 52 may be provided with at least two grids 70 placed opposite the ejection device outputs 57, 58 made for example from Pt plate alloys (about 50%) with rhodium, rhodium, palladium, iridium and other palladium Elements to improve the efficiency of the installation.
The device provides an Orbeli catalyst for obtaining high-quality hydrocarbons, consisting of osmium Os, rhodium Rh, beryllium Be and lithium Li, the percentage of which is proportional to the atomic masses. An alloy obtained from said elements is used to make nets 70.
The condenser-cooler 7 of the known design is advantageously designed to collect methanol raw material and is provided with additional conduits 71 and 72 with drive valves 73 and 74. The conduit 71 with the drive valve 73 is designed to drain methanol, and the conduit 72 with the drive valve 74 is for withdrawing unreacted gases through Check valve 75 to the inlet of turbocharger 1 or to the main pipeline (not shown).
By varying the process conditions, for example, by changing the temperature or pressure, the condenser-cooler 7 may be provided with a separator and collectors for the desired hydrocarbon products (not shown conditionally), with unreacted gases from the separator passing through the check valve 75 to the inlet of the turbocharger 1.
To conduct the process, the methanol production unit is equipped with commercially available automation means, in particular, by measuring and controlling the pressure at the outputs of the turbocharger 1 and the oxygen blower 3, by means of measuring and controlling the temperature, by means for measuring and controlling the methane: oxygen volume ratio equal to (0, 7-2,1): 1.
The sampling devices 76, 77 for measuring the pressure at the outputs of the turbocharger 1 and the oxygen blower 3 are installed in conduits 16 and 21. The temperature sampling devices 78 and 79, for example thermocouples, are installed in conduits 35 and 48. The sampling devices 80 and 81 Methane and oxygen are installed in front of the reactor 6 in the pipelines 35 and 48.
Secondary instruments with regulating devices for measuring and controlling pressure and temperature are located at the control station 8. The selective devices 80 and 81 are connected via the regulator 82, the methane: oxygen ratio, the control station 8 to the driving rotary shutters 17, 23.
To isolate the hydraulic bonds between methane and oxygen, an additional non-return valve 83 is installed in conduit 48.
The ratio of methane: oxygen, equal to (0.7-2.1): 1, is selected from the calculation of the lack of oxygen in the interaction of methane with oxygen in the reactor 6, which increases the efficiency and safety of the installation.
The proposed plant for the production of methanol meets all the requirements for the design and operation of chemical plants.
INSTALLATION FOR PRODUCTION OF METHANOL WORKS AS FOLLOWING
In the initial position, the units and regulators of the plant are disconnected from the power sources, pipelines 2 and 4 are closed from the sources of methane and oxygen by actuating valves (gate valves) 13, 22.
In order to activate the battery units in accordance with a predetermined control algorithm, control valves of the control station 8 open the drive valves 13, 14 through a predetermined amount, through which methane enters the compressor and into the combustion chamber 15 of the turbocharger 1. Known methods are the launch of a turbocharger 1, which drives the compressor and the alternator 9. Turbocharger 1 is first outputted to minimum rotations and then to nominal ones, while simultaneously by the control signals of control station 8, the rotary shutters 17, 23 are set to the middle position, and the drive valves 67, 68 and 74 are opened to a predetermined value. From the turbocompressor, 1 methane at a pressure of 7.5 MPa is pumped through the conduit 16 to the gas preheater 5, and then through the line 35 to the reactor 6, in which the methane stream is accelerated by the ejector device 57. From the reactor 6, methane under pressure is pumped through the openings 69 of the co- , The annular cavity 63 of the casing 62, the conduits 64, 65 and 66 and the drive valves 67, 68 to the condenser cooler 7. From the condenser-condenser 7, methane through the drive valve 74 and the non-return valve 75 of the pipeline 72 returns to the inlet of the turbocharger 1.
The installation establishes the process of methane circulation. Servicing personnel check the hermetic connections of the installation.
At the same time, the energy flow from the power supply 9 is supplied to the control station 8 via a rectifier 10. The oxygen pump 3 switches on via the control signals of the control station 8 and through the voltage regulator 11 the gas preheater 5. An oxygen pressure of 7.5 MPa at the outlet 46 of the supercharger 3 is achieved by controlling the rotations of the DC electric motor 19.
When the gas heater 5 is turned on, the electric current, flowing through the sections 39, 40, heats the housings 37, 38 of the sectional thermal electric heater 32, the heat from which is transferred to the direct-flow heat-conducting pipe 27 and to the pipes 50 of the thermal-conducting oxygen converter 33 via a plurality of plates 51.
Due to convection and radiation from heated pipes, 27, 50 methane and oxygen are heated in the range of 350-400 ° C. Temperature change control both in body cavity 24 and in conduits 35 and 48 is carried out by thermocouples 78 and 79 (thermocouples in housing 24 are not shown conditionally ) With the signal output to the control station 8. The temperature monitoring and control system ensures that the set temperature is maintained within the specified range.
Heated oxygen is pressurized under pressure into the reactor 6, in which the oxygen flow is accelerated by the ejecting device 58. At the same time, the methane-oxygen flow control system maintains a predetermined ratio of gases.
The signals from the prefabricated devices 80, 81 are fed to the ratio controller 82, at the signals of which the control signals for changing the position of the rotary shutters 17, 23 are generated in the control station 8.
The counter movement of the heated gas streams leads to intensive mixing and interaction of methane and oxygen, as a result of which direct homogeneous oxidation of methane with oxygen is carried out in the reactor 6 to obtain methanol.
Current flows of gases in the reactor 6 are mixed together in its middle part. A small volume of a mixture of gases, for example one third, enters the condenser-cooler 7 by the above-described methods, and a large volume of gases due to the presence of a hydraulic resistance (the hydraulic resistance is controlled by the drive valves 67, 68) flows in the reverse direction due to the presence of gas suction through the annular gaps 59 ejecting device 57, 58 from the wall areas of the reactor, then the flow of the gas mixture is again accelerated by the ejecting devices.
Thus, the circulation of the gas mixture is maintained in the reactor 6. When the catalyst nets 70 are used in the reactor 6, the process of interaction of methane and oxygen is enhanced, and the oxidation rate increases.
The following reactions occur in the reactor 6:
In this case methane and oxygen are mixed in a ratio (follows from the formula) 2: 1, however, to obtain a wide class of organic compounds, the volume ratio can be chosen (0.7-2.1): 1.
If biogas is used for the production of methanol, biogas is first passed through a separator to remove CO 2 , CO, N and H 2 S from the mixture, and then purified CH 4 methane is fed to the inlet of turbocharger 1.
In the condenser-condenser 7 condensation of the vapor of gaseous methane and other hydrocarbons into a liquid state occurs. The process of condensation occurs at normal temperature and pressure 
. Unreacted gases are preheated by the heat generated by the condensation of methanol vapor and are supplied through the drive valve 74 and the check valve 75 to the inlet of the turbocharger 1. The process is performed cyclically.
For optimum process control, a gas analyzer (not shown) is installed in the pipeline 72 to determine the percentage of oxygen in the unreacted gases. The gas analyzer generates a correction signal, which is introduced into the ratio controller 82.
Periodically, the methane is expelled from the condenser-cooler 7 through the drive valve 73 for further processing.
The technical and economic efficiency of the methanol plant lies in the fact that, thanks to a new set of essential features, the object of the invention is achieved, in particular, the plant productivity is increased through the use of new devices - a gas heater 5 and a reactor 6, gas methanol being produced not only in the reactor 6 , But also in the technological chain: in the straight-through heat-conducting pipe 27 of the gas preheater 5, in the pipeline 35 due to the interaction of unreacted gases.
In addition, the proposed plant for the production of methanol is universal and can be used, for example, for the production of formaldehyde and other target products due to changes in the conditions of the process.
CLAIM
A plant for the production of methanol, comprising technological pipelines for supplying methane and oxygen by a turbocharger and a supercharger through a gas preheater to a reactor made in the form of a straight-through pipe and connected to a condenser-condenser, the latter being connected by an additional process pipeline to the turbocharger inlet and a control station, That it is provided with ejecting devices, a casing covering the middle part of the rectilinear reactor tube, and a check valve installed in the additional process pipeline, the gas heater is made in the form of a cylindrical body insulated from the external environment in which a straight-through heat-conducting pipe is mounted, which is connected at one end to the outlet of the turbocharger , And the other end to the inlet of a straight-through reactor tube, a sectional thermal electric heater electrically connected via a voltage regulator to a power supply and mounted in a heat conducting body contacting a straight flow heat pipe, and a thermal conductive oxygen converter communicating with its inlet to the oxygen blower outlet, and Outlet with an additional inlet of the reactor located at the other end of the straight-through pipe, the section of the middle part of the straight-through pipe of the reactor having a perforation and forming, together with the casing, an annular sealed cavity communicating by conduits with a condenser-condenser, and ejecting devices are installed in the inputs of the rectilinear reactor tube.
The plant of claim 1, wherein the heat-conducting oxygen converter is made in the form of two hollow rings, one of which is communicated with the discharge of the oxygen supercharger and the other with an additional reactor inlet, the rings communicating with each other by straight-through pipes surrounding the thermal electric heater.
The plant according to claim 1, characterized in that the portion of the middle part of the rectilinear reactor tube is provided with at least two grids placed opposite the ejection device outlets and made of a platinum alloy.
The plant according to claim 1, characterized in that the gas heater is provided with heat-conducting plates contacting the electric heater body and the straight-through pipes of the heat-conducting oxygen converter.
print version
Date of publication 03.11.2006гг
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