Method for preparing methanol from gas in gaseous and gas-condensate deposit

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing methanol. Method involves the successive feeding hydrocarbon-containing gas, injection of chemically purified water, carrying out the preliminary steam reforming for preparing synthesis gas and carrying out the final reforming if formed gas with addition of oxygen under pressure for carrying out synthesis of methanol, heating reactor for preliminary reforming by flow of obtained synthesis gas going out from reactor for the final reforming that is fed to intertubular space of reactor for preliminary reforming followed by cooling synthesis gas obtained as result of reforming by vapor-gas mixture and carrying out synthesis of methanol in 2-step reactor. Cooling the reaction mixture for carrying out isothermal reaction for synthesis of methanol in intermediate external heat exchanger of two-step reactor is carried out with vapor-gas mixture and cooling flow going out from reactor for synthesis of methanol is carried out with vapor-gas mixture and chemically purified water. Also, invention relates to unit for preparing methanol including the source of hydrocarbon-containing gas and unit for complex preparing gas, reactor for preliminary vapor reforming heated with flow going out from reactor for final reforming, two-step reactor for synthesis of methanol, heat exchangers for cooling synthesis gas, heat exchangers for cooling flow going out from reactor for synthesis of methanol, separator for separation of reaction products and exhausting gases and crude methanol. The unit for preparing methanol is assembled with unit for complex gas preparing including block for preparing chemically purified water, block for preparing raw, additional manufacture involving torch making, cleansing constructions, sources of electric energy, air of control and measuring instruments and automatic equipment, chemical laboratory and operating block. Two-step reactor for synthesis of methanol joined with heat exchanger for cooling synthesis gas with vapor-gas mixture, intermediate external heat exchanger for cooling the reaction mixture with vapor-gas mixture is joined in-line with heat exchanger for cooling flow obtained in reactor with vapor gas mixture, heat exchanger for cooling of chemically purified water and separator for separation of reaction products. Ignition device is assembled in reactor for final reforming that promotes to carry out the start of unit without trigger furnace. Water is injected in flow hydrocarbon gas directly before heat exchanger for the reaction mixture that provides excluding boiler-utilizer and trigger boiler from schedule and to solve the problem for cooling the reaction mixture in reactor for synthesis of methanol also. Based on integration of the device for preparing methanol in technological schedule with unit for complex preparing gas and significant change of the conventional schedule for preparing methanol method provides 3-fold reducing capital investment.

EFFECT: improved method for preparing methanol.

2 cl, 1 dwg

 

The present invention relates to the field of organic chemistry, in particular to technology for methanol production via synthesis gas.

The main gas and gas condensate field located in remote areas Far North of the Yamal-Nenets Autonomous district, Krasnoyarsk region and Yakutia. Today, natural gas production in the amount of up to 85% is produced in the North of the Tyumen region on major fields: such as Urengoy, Yamburg, polar, which has entered a declining production. Further increase and maintain production volumes of natural gas will be mainly carried out at the expense of numerous small fields. Mainly on the profitability of such deposits is affected by the cost of hydrate inhibitors (up to 2.5 kg per 1000 m3gas condensate fields), in which methanol is used. Delivery of methanol 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 in field conditions in the installations of complex gas treatment plants) would allow to solve the above problems for manufacturers of gas and gas condensate.

The number of known ways of converting methane to methanol. Broad industry the military application have the following technologies:

- steam reforming of methanol synthesis gas (mixture of CO, CO2N2for large-scale production of methanol, more than 1000 tons/day, followed by catalytic conversion to methanol (licensed production company Davy Progress Tegnology UK, AG Lurgi", AG "Linda", GIAP of the Russian Federation and others);

- autoreporting methane in the synthesis gas with a preliminary block steam reforming of methane and finally oxidized in the reactor autoreporting oxygen supply, and further catalytic conversion to methanol (has a license AG Lurgi"), which can be used for medium (500 tons/day) and large-scale production the production of methanol;

is the process "Tandem" developed by Russian developers GIAP, the license of which is sold to a company AG "Linda", the process is based on the production of synthesis gas in 2 reactors, the heat of oxidation reaction of methane with oxygen is used in a tubular reactor steam reforming process is used for medium (500 tons/day) and larger productions.

These technologies are described in many publications and presentation materials of the above companies. For the implementation of these processes it is necessary to have sophisticated equipment, high demands on the purity of the gas, and the high cost of electricity for production of synthesis gas and its treatment, the use of expensive gas compressors unprofitable small plants with a capacity of less than 500 tons/day.

Currently, the greatest interest is direct, bypassing the stage of synthesis gas production, gas-phase oxidation of methane to methanol at high pressures. The process is carried out at pressures up to 10 MPa and temperatures of 400-500°in tubular reactors with a relatively low initial concentrations of oxygen, followed by cooling gas-liquid mixture and separation of liquid products, of which the rectification into methanol (Arutyunov B.C., O.V. Krylov "Oxidative conversion of methane", Moscow, "Science", 1998, RU AND 2049086; GB 2196335; SU A1, 1469788; EN A, 2162460, 2203261). The above known methods partial direct oxidation allow you to create small-scale production of methanol. The main disadvantages of this production are: obtaining raw methanol concentration was low, the production of large quantities of by-products such as formaldehyde, acetic acid and others, which in turn are not implemented in field conditions, and for disposal degrade the environment and cause harmful effects on the equipment, thus reducing its corrosion resistance, which in turn makes this method of producing methanol uncompetitive.

The closest to the proposed method is to obtain a methanol technology GIAP RF (patent 803191, 784148).

Necessary for synthesis of meta the Ola synthesis gas obtained by the method of steam reforming using a combined scheme of the tubular reactor and the shaft of the reactor. The name of the system reforming of natural gas "Tandem".

In a tubular reactor are pre-conversion of methane and other hydrocarbons in natural gas by using the heat of the reformed gas after the shaft of the reactor.

Technological scheme of production of methanol comprises the following main stages of the process:

- block of raw material preparation, raw material. purification from sulfur compounds;

- steam conversion of natural gas under pressure 2-3,5 MPa and at a temperature 510-600°in a tubular reactor, 700-850°in the shaft reactor with heat recovery system converted gas;

- compression and circulation converted gas syngas compressor driven by a steam turbine or electric motor;

- synthesis of methanol under a pressure of 6.0-8.0 MPa and at a temperature of 220-280°With the radial reactor of the type using a heat of fusion in remote heat exchangers for preheating feed water or steam generation; distillation of crude methanol in two columns using the reformed gas heat with obtaining methanol-rectified specified quality;

auxiliary enterprises (deaeration of demineralized water to obtain the feed water, waste heat boilers, the starting of the boiler feedwater pump, the moustache is the time of preparation of additives to the feed water, the Stripping process condensate under pressure using a Stripping gas in the process of starting the furnace, treatment facilities etc).

The use of this equipment makes the process costly and unprofitable for small-scale installations.

Given these factors, it can be stated that the market for the production of methanol there are no competitive small units of production of methanol.

Consider as an example the composition of the medium installation GIAP, which consists of blocks of raw material preparation (removal of sulfur compounds), process Tandem to produce synthesis gas (mixture of CO, CO2H2), the methanol synthesis reactor, unit training chemical water purification, block compression of air, oxygen-enriched, block distillation of methanol, heat exchangers, air coolers, start-up boiler to produce steam, boiler steam, tank, auxiliary production.

Methanol production can be divided into the following blocks on capital investments:

- preparation unit gas - 13-17%;

- block the synthesis gas production is 25-30%;

- block the synthesis of methanol - 10-12%;

block distillation of methanol - 15-20%;

- preparation unit chemically treated water - 4-6%;

- the comp is isorna device for compressing and circulating synthesis gas 4-8%;

- heat recovery unit steam - 8-10%;

- preparation unit oxygen - 6-8%;

- starting the boiler and starting the oven - 6-8%;

- auxiliary production by 10-15%.

The goal is to create small units for methanol production via synthesis gas (mixture of CO, CO2H2) is solved by integrating with the installation of complex gas treatment plant (GTP), where methanol is used as hydrate inhibitors in the system of gathering, processing and long-distance transportation of gas. Integration scheme of the installation for production of methanol with the unit allows you to reduce capital expenditures on the plant for production of methanol is several times compared with the traditional methods and greatly reduces the cost of production of methanol.

The problem is solved yet due to:

- exceptions block of training materials as gas, prepared to unit fields of the Far North and East of the Russian Federation, does not contain sulfur compounds which poison the catalysts synthesis gas and methanol synthesis (reporting materials OOO "TyumenNIIgiprogaz", OOO "VNIIGAZ", JSC "Gazprom" and reference fields);

exceptions to the recovery boiler for generating steam by injecting water into the gas flow through the nozzle directly in front of heat exchanger cooling of the products of the synthesis reactor, the methane is La, and to use this gas mixture with a temperature of 120-150°for intermediate cooling of the reaction mixture of a methanol synthesis reactor;

- exception starting the boiler to produce steam, as water is injected directly into the gas flow;

- exception starting the furnace for heating the gas mixture to a temperature of beginning of the process for production of synthesis gas by mounting in the shaft reactor special igniter;

exceptions to the compressor for compressing and circulating synthesis gas by the process for production of synthesis gas at a pressure equal to the pressure of synthesis of methanol;

- exceptions block distillation of crude methanol, because the high concentration methanol to 78-84% allows the use of methanol raw as hydrate inhibitors;

- exceptions block preparation of chemically treated water, because the block of preparation of chemically purified water available on GPP;

- exceptions auxiliary production (torch facilities, treatment facilities, sources of electric power, Instrument air, control room, chemical laboratory, etc), since these structures are part of the unit.

Thus, by integrating small units of production of methanol in the composition of the unit and due to the significant changes in the traditional scheme of obtaining IU is anola (excluding boiler, starting the boiler, starting the furnace, compressor, etc.) is almost 3-fold reduction of capital investments, which in turn makes this method of producing methanol quite competitive offer. The conditions of the ratio of the capacity of the unit and installation of the production of methanol remain unchanged, because the specific consumption of methanol at 1000 m3gas for almost all fields are approximately equal.

The task is also solved by the fact that hydrocarbon gas unit with a temperature of 20°C, cooling in the heat exchanger "gas-gas" reaction mixture for methanol synthesis, where in the stream immediately before the heat exchanger is injected through the nozzle chemically purified water, to the extent necessary for carrying out the process of pre-steam reforming in a tubular reactor, then the steam-gas mixture flows into the intermediate heat exchanger of the methanol synthesis reactor to maintain the temperature of the methanol synthesis in isothermal mode. Gas-vapor mixture after cooling products for the synthesis of methanol is sent to the heat exchanger gas-gas for quenching (overheating) and for cooling the products of the synthesis gas prior to methanol synthesis reactor. After quenching the gas-vapor mixture with a temperature of 380-430°enters the tube space of the tubular reactor is seat reservation steam reforming, tubes which are filled with Nickel catalyst K-905 GIAP-16. Formed in the reforming gas is transferred to the next stage of the reformer, which produces the final synthesis gas by adding oxygen, and then this hot gas is used to heat the tubes with the catalyst at the initial stage of reforming. The formation of synthesis gas in the shaft reactor occurs at a temperature of 600-950°and at a pressure equal to the pressure of synthesis of methanol. During the process flow around the following main reactions:

CH4+H2O=CO+3H2

CH4+2O2=CO2+2H2O

CO+H2O=CO2+H2

and other

The resulting synthesis gas after cooling in the heat exchanger quenching the feedstock with a temperature of 250-280°comes in 2-step isothermal reactor for methanol synthesis.

For the process of methanol synthesis (CO+2H2=CH3HE + heat CO2+3H2=CH3HE+H2O + heat) the reactor is filled with a copper-containing catalyst SNM-3C. The reaction of methanol synthesis proceeds with the formation of heat and to conduct isothermal process, the reactor is 2-stage, with external heat exchanger for intermediate cooling of the reaction mixture. The reaction of methanol synthesis occurs when the tempo is the atur 220-280° C. the Resulting reaction mixture is directed to the cooling in the heat exchanger "gas-gas" and then for the final cooling of the gas-liquid", where as a cooling agent used chemically treated water, which then is sent to injection into the gas stream for the purpose of conducting pre-reforming. The cooled reaction mixture with a temperature of 20-35°enters the separator for separating methanol from the unreacted products synthesis gas. Methanol-Syrets concentration 78-84% goes to Park storage of methanol, and the gases from the separator mainly containing a CH4H2and CO2sent to use for own needs unit (boiler, power plant and other heaters) or mixed with the prepared gas treatment unit, and due to the small amounts of unreacted gas on the quality of prepared commercial gas unit no effect.

The main difference of this method from the traditional ways of production of methanol via synthesis gas (steam reforming, combined reforming process "Tandem") is that by integrating plant for methanol in the composition of the unit is achieved almost 3-fold reduction of the set of equipment and capital investments for the production of methanol as a hydrate formation inhibitor, as well as a significant reduction in exploitation costs by reducing energy consumption (excluded compressor unit for compressing and circulating synthesis gas, starting the boiler and starting the furnace, boiler, installation preparation of chemically treated water).

Due to the absence of harmful emissions from the process is environmentally friendly production.

Further, the invention is illustrated with specific examples of its implementation and the accompanying drawing, which shows a General view of the installation for the production of methanol.

Device for producing methanol includes 2-stage reactor 7 for the reaction of methanol synthesis with external heat exchanger 3 for cooling the reaction mixture to conduct isothermal reaction, which is connected through the heat exchanger "gas-gas" 4 reactor 5 pre-steam reforming in the form of a tubular reactor, where the tubes are filled with catalyst, annulus separates the tube Board, hot synthesis gas from the reactor final reforming. For the final reforming reactor 6 has a mixing device for mixing gases pre-reforming with oxygen supplied by the igniter to start the installation, as well as the reactor 6 is filled with the catalyst, the top layer of the catalyst is protected by ceramic tiles (balls) from baking catalyst. Oxygen is supplied with the unit to produce oxygen, which is supplied complete, the Reaction mixture from the reactor 7 for cooling is fed into the tube space of the heat exchanger the gas-gas 2, annulus which is the hydrocarbon gas with the installation of complex gas stream which is injected chemically purified water is directed from the heat exchanger gas-liquid 8, the cooled reaction mixture to a temperature of 20-35°into the separator 9 for separation of methanol, methanol-raw goes to the Park store for future use, and unreacted synthesis gas is returned to unit for use on their own needs or the mixture of product gas.

Example, confirming the ability of the proposed method of producing methanol.

Cold hydrocarbon gas unit 1 with a flow rate of 906,8 kg/h at a pressure of P=8.0 MPa passes through the heat exchangers 2, 3, 4, where it is heated to 380-430°With, in the stream which the heat exchanger 2 in the amount of 1150 kg/h is injected chemically purified water, the mixture enters the reactor 5 pre-steam reforming in the tube space, then the resulting gas pre-reformer is directed to the final reforming in a reactor 6 which is supplied with oxygen in the number 743,5 kg/hour, then the reaction mixture with a temperature of 750-900° through the reactor 5, the heat exchanger 4, the temperature 220-280°into the reactor 7 for methanol synthesis, methanol synthesis proceeds at a pace which the atur 230-280° C and pressures up to 8.0 MPa. Next, the reaction mixture through the heat exchangers 2, 8 enters the separator 9, the unreacted gas in the number 1356,5 kg/hour routed to the unit for their own needs, methanol raw 78-84% concentration in number 1439,3 kg/h goes to the Park.

1. A method of producing methanol, comprising the sequential flow of hydrocarbon gas injection chemically treated water, prior steam reforming to produce synthesis gas, the final reforming gas formed by adding oxygen at a pressure equal to the pressure of synthesis of methanol, heating the reactor pre-reforming flow produced synthesis gas exiting the final reactor of the reforming served in the annulus of the reactor pre-reforming, further cooled synthesis gas obtained by reforming, steam-gas mixture and the synthesis of methanol in a 2-stage reactor, characterized in that the cooling of the reaction mixture for carrying out isothermal reaction methanol synthesis in the intermediate external heat exchanger two-stage reactor was carried out by gas-vapour mixture, and cooling flow coming from the synthesis reactor m is canola, carry out gas-vapor mixture and chemically treated water.

2. Installing the production of methanol containing a source of hydrocarbon gas from a plant of complex gas preparation, the preliminary reactor steam reforming, the heated stream exiting the final reactor of the reforming unit, a two-stage methanol synthesis reactor, heat exchangers cooling the synthesis gas, heat exchangers cooling flow coming from the methanol synthesis reactor, a separator for separating the reaction products in the exhaust gases and methanol raw, characterized in that the installation of the production of methanol integratedwith the installation of complex gas treatment plant (GTP)that contains the block of preparation of chemically treated water, the block of preparation of raw materials, auxiliary production, including flare production, treatment facilities, sources of electric power, Instrument air, chemical laboratory, control room, and a two-stage methanol synthesis reactor, connected to a heat exchanger cooling the synthesis gas by gas-vapour mixture, equipped with an intermediate external heat exchanger cooling the reaction mixture by gas-vapour mixture and successively connected with heat exchanger cooling obtained in the reactor flow gas-vapor mixture, heat exchanger cooling chemically purified water and separate the rum for the separation of reaction products.



 

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FIELD: technology for production of methanol from syngas.

SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.

EFFECT: simplified method due to process optimization.

12 cl, 3 tbl, 3 dwg

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FIELD: technology for production of methanol from syngas.

SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.

EFFECT: simplified method due to process optimization.

12 cl, 3 tbl, 3 dwg

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Reactor // 2246345

FIELD: chemical industry, catalytic processes.

SUBSTANCE: the invention presents a reactor for catalytic processes and is dealt with the field of chemical industry and may be used for catalytic processes. The reactor contains: a body; units of input and output for a reaction mixture and products of reactions; units of loading and unloading of a catalyst; a catalyst layer with the groups of the parallel hollow gas-permeable chambers located on it in height in one or several horizontal planes and each of the chambers has a perforated gas-distributing pipe with impenetrable butt connected to the group collector and used for input of additional amount of the reaction mixture. Each of perforated gas-permeable chambers is supplied with the second gas-distributing pipe with impenetrable butt. At that the impenetrable butts of the pipes are located on the opposite sides. The given engineering solution provides uniformity and entirety of agitation of the reaction mixtures.

EFFECT: the invention provides uniformity and entirety of agitation of the reaction mixtures.

5 cl, 4 dwg

The invention relates to the field of chemical technology

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