A method of producing methanol

 

The invention relates to a method for producing methanol, which is used for gas production. The method includes separate feeding into the mixer first reaction zone of the reactor purged from drops and solid dispersion of pollution of natural gas under the pressure of 10-100 ATM, preheated to a temperature of 300-500oWith, and oxygen-containing gas, including air, under pressure of 10-100 atmospheres and at a temperature of 40-50oWith that turbulent mixing of the gases in the mixer first reaction zone and the oxidation for a time of 0.2 to 10 s at a temperature of 370-470oC and the oxygen concentration is not more than 1.5 vol.%, with the subsequent turbulent mixing of the gases in the mixer of the second reaction zone of the reactor and oxidation in her oxygen-containing gas supplied to the mixer of the second reaction zone for a time of 0.2 to 10 s at a temperature of 370-470oWith that in doing so, a uniform heating of the gas to the temperature of the reaction simultaneously with turbulent stirring consistently mixers both reaction zones, with subsequent cooling of the reaction mixture, after leaving the second reaction zone of the reactor, in the regenerative heat exchanger natural gas with the flue gases. When this oxidation PE is a simple filler, placed in the reaction zone, and the concentration of oxygen in the second reaction zone 2-12 vol.%, and the time of passage of the gas through an inert porous filler exceeds the time of diffusion of the reaction products to its well-developed inner surface, and the gas flows in the reaction zones create a counter-current relative to the direction of their flow, while providing a continuous heat transfer through the walls of their side surfaces. The method allows to increase the selectivity and methane conversion in a single pass reactor, to ensure continuity besidethe mode gas production due to continuous operation unit of methanol with the accumulation and subsequent continuous feed unit and/or in the loop gas field. 4 C.p. f-crystals, 1 Il.

The invention relates to the field of organic chemistry, and in particular to methods for the production of methanol used for gas direct gas-phase oxidation of methane, and can be used for the preparation of hydrocarbon gas to transport oil and gas industry.

The number of known methods for producing methanol by steam reforming of methane in the reactant gases with the formation of a mixture of CO and H2at high temperature and sinteticheskogo methanol, M.: Chemistry, 1984, S. 72-125 [1]).

This technology has several disadvantages, namely high demands on the purity of gas, large inputs for production of carbon monoxide and hydrogen, as well as the lack of profitability of small and medium enterprises with a capacity of less than 300000 tons/year.

Known methods for producing methanol on-site installation of the integrated gas transport and natural gas field to eliminate condensation in the wells and flowlines (T. M. Bekirov and A. I. Shatalov, Collection and preparation for transport of natural gas, M.: Nedra, 1986, S. 259, [2]).

Also known a method of directly, bypassing the stage of obtaining reagents, gases, gas-phase oxidation of a hydrocarbon gas (methane) in methanol at pressures up to 100 atmospheres and a temperature of from 300 to 500o(C. S. Arutyunov, V. I. Bacevich, C. I. Vedenev, Direct gas-phase oxidation of natural gas at high pressures in the methanol and other oxygenates, J. USP, 1996, T. 65, 3, S. 211-241 [3] ).

A known method of producing methanol, comprising separate feeding into the mixer natural gas (methane) and oxygen-containing gas, including air, the subsequent filing of turbulent peremeshennoi mixture in the reactor with inert inner surface, gas-phase oxide is provided a catalyst when the oxygen concentration of 2-20 vol.%, the separation of methanol from the reaction products by cooling with condensation, the recirculation exhaust the reaction gas with unreacted methane in the first reactor or the feed for the second subsequent reactor (U.S. Patent 4618732, class C 07 C 29/48, 1986 [4]).

The disadvantage of this method is a great response time and low productivity methanol, which practically does not allow its use for commercial production of the target product by direct oxidation of natural gas to methanol to gas at high pressures and temperatures.

The closest in technical essence and the achieved effect is a method of producing methanol, comprising feeding into a mixer first reaction zone of the reactor purged from drops and solid dispersion of pollution of natural gas under the pressure of 10-100 ATM, preheated to a temperature of 300-500oWith, and separate feeding into the mixer first reaction zone of the reactor oxygen-containing gas, including air, under pressure of 10-100 ATM and at 40-50oWith that turbulent mixing of the gases in the mixer first reaction zone and the primary oxidation in her time of 0.2-10 when 370-470oC, a pressure of 10-100 ATM and the oxygen concentration is not more than 1.5 vol.% of the th without pre-cooling the gas stream during the 0.2-10 with 370-470oWith 10-100 atmospheres and at high oxygen concentrations, additionally supplied to the mixer of the second reaction zone, use the target product for gas production and the flow of exhaust gases in the original natural gas. (RF patent 2057745, class C 07 C 29/50, 31/04, 1996, [5]) (the prototype).

The disadvantage of the method described above is the low selectivity for yield of methanol, and a small degree of methane conversion in a single pass reactor with two reaction zones, which limits its performance methanol and accordingly makes commercial use for the production of methanol on-site installation of the integrated gas transport and natural gas field to eliminate condensation in the wells and flowlines.

The technical result of the proposed method for the production of methanol for gas production is to increase the selectivity of the process of direct gas-phase oxidation of methane and methane conversion in a single pass reactor with two reaction zones for the installation of complex gas treatment plant (GTP) or for submission of produced methanol in the loop (hole) gas fields, as well as the continuity besidethe mode gas the unit and/or in the train.

To achieve the technical result in the method of producing methanol, comprising separate feeding into the mixer first reaction zone of the reactor purged from drops and solid dispersion of pollution of natural gas, under the pressure of 10-100 ATM, preheated to a temperature of 300-500oWith, and oxygen-containing gas, including air, under pressure of 10-100 atmospheres and at a temperature of 40-50oWith that turbulent mixing of the gases in the mixer first reaction zone and the oxidation for a time of 0.2 to 10 s at a temperature of 370-470oC and the oxygen concentration is not more than 1.5 vol.%, with the subsequent turbulent mixing of the gases in the mixer of the second reaction zone of the reactor and oxidation in her oxygen-containing gas supplied to the mixer of the second reaction zone for a time of 0.2 to 10 s at a temperature of 370-470oWith that in doing so, a uniform heating of the gas to the temperature of the reaction simultaneously with turbulent stirring consistently mixers both reaction zones, with subsequent cooling of the reaction mixture, after leaving the second reaction zone of the reactor, in the regenerative heat exchanger natural gas, characterized in that the oxidation in the first and second reactionnary in the reaction zones, when the concentration of oxygen in the second reaction zone 2-12 vol.%, at the same time passing the gas through an inert porous filler exceeds the time of diffusion of the reaction products to its well-developed inner surface, while the gas flows in the reaction zones create a counter-current relative to the direction of their flow, while providing a continuous heat transfer through the walls of their side surfaces.

In addition, turbulent mixing and simultaneous heating of the gases to the reaction temperature, passing through the porous filler is carried out at a Reynolds number equal to Re=VD/2=100-10000, preferably at 1000-5000, and the characteristic pore size of the filler is D=(0.01 to 10)L, preferably of 0.1-1)L, where,andrespectively the density, dynamic viscosity and the degree of turbulence of the gas flow, V=Q/S, its linear velocity, Q is the volume flow of the gas stream in the reaction zone, L and S are respectively the thickness and the front along the geometric flow area of the porous filler.

To eliminate losses methanol is evident mixture of at least 150-200oWith regenerative heat exchanger, the cooled natural gas stream from the installation of complex gas treatment plant (GTP) or loop.

Finally, divide after the reactor gas stream into two, one of which served with the target product in the installation of complex gas and/or train, and from another thread selected target product by cooling and condensation with subsequent rectification and submission to accumulate in the installation of complex gas.

In the first reaction zone by passing a mixture of natural gas and oxygen with a concentration of not more than 1.5% vol. through the porous filler is a high-speed, turbulent, uniform (marginal) mixing with simultaneous uniform heating of the mixture to the reaction temperature. The process of mixing and equalization of the temperature profile is carried out at a Reynolds number Re=VD/2=100-10000, preferably at 1000-5000, and the characteristic pore size of the filler is D=(0.01 to 10)L, and the time of passage of the gas through the porous filler should be less than the time of diffusion of the reaction products and molecules of methane to its well-developed inner surface. Due to the implementation of the CSO temperature profile as length, and the section of the first reaction zone, at a low oxygen concentration starts razvetvlenno chain reaction with subsequent formation of the desired product with high selectivity for methanol compared to the release of formaldehyde and water at low concentrations of the products of deep oxidation of methane, primarily carbon oxides (CO, CO2) and hydrogen.

In the second reaction zone by passing a gas stream with a volume concentration of oxygen 2-12% through the porous filler perform high-speed, uniform mixing of the mixture of gases in the turbulent regime with simultaneous uniform heating by heat exchange with filler. The process of mixing and equalization of the temperature profile is carried out at a Reynolds number Re=VD/2=100-10000, preferably at 1000-5000, and the characteristic pore size of the filler is D=(0.01 to 10)L, and the time of passage of the gas through the porous filler should be less than the time of diffusion of the reaction products and molecules of methane to its well-developed inner surface. The flow directions of the gas flow in coaxial, the reaction zone through the porous fillers create PR is nutnosti in the second reaction zone through the use of porous fillers and coaxial arrangement of the first reaction zone inside the second oxidation zone and create conditions quasihistorical reactions in both zones. This allows the oxidation reaction in the second zone at elevated compared with the prototype concentrations of oxygen supplied to natural gas, and accordingly to increase the conversion of methane almost without reducing the selectivity of the output of methanol in a single pass dual-zone gas through the reactor. This result agrees well with the calculated data on gas-phase oxidation of methane in kvazistaticheskikh conditions, difficult-to-implement in practice in reactors with one and/or two (as in the prototype) are consistently defined and separated along the flow zones of oxidation without the porous filler [3,5].

Experimentally observed instability of the process of gas-phase oxidation of methane unwanted invalid when industrial production of methanol by direct oxidation of natural gas [1, 3-5]. In particular, it is known [1, 3-5] that the instability of the process due to holodnoplamennym and vibrational modes of oxidation, the heterogeneity of the temperature profile, as well as a significant scale turbulence, partially commensurate with the dimensions of the reaction zone. In this regard, in the second reaction zone, the gas stream is passed sequentially through a cascade of separated layers of porous inert the population of natural gas by reducing turbulence scale increasing the degree of turbulence of the flow and temperature uniformity, elimination of vibrational modes of oxidation in the reaction zone.

At the outlet of the second reaction zone of the gas flows into the annulus recuperative heat exchanger, where it gives up heat to the cold flow of natural gas from the plume and/or unit with decreasing temperature, the reaction mixture is not less than 150-200oC. resulted In a significant cooling of the mixture selectivity exit methanol is not reduced in the heterogeneous interaction of molecules of methanol with the surface of the reaction zone and connecting pipes, i.e., there is a quenching of the reaction products with preservation of their stoichiometric composition.

For the production of methanol with a concentration of from 75 to 95 wt.% the gas flow is divided into two. One of the threads with gaseous methanol product is sent to the unit and/or in the loop, and the other stream is cooled in the cooler-condenser with the condensation of liquid products (methanol, mixed with ethanol, water, acetone, propanol, formaldehyde, acetic and formic acid and so on ). The obtained gas-liquid mixture is passed through a separator and then is subjected to rectification. The purified natural gas is mixed with another Potala from 75 to 95 wt.% gather in the capacity of the unit and, if necessary, additional use for example, in the accident the reactor to eliminate processes hydrocortosone with increasing moisture content, significant emissions of water with the formation of the liquid droplet and/or by lowering the temperature of the produced gas by the standard method [2]. As is known, the unit must be an emergency supply of methanol at 30-40 days of continuous gas production and gas transport [2].

As a result, in the proposed method increases the selectivity for yield of methanol to 60-70 wt.% when the degree of conversion of methane to 10 vol.% in a single pass through the reactor with two coaxial reaction zone with a porous filler, which is more than 1.2-1.5 times higher than the data of the prototype on the selectivity of methanol and methane conversion. In addition, this method allows you to create a buffer stock of methanol in case of emergency (emergency) situations, and consequently to carry out a continuous gas production and subsequent continuous gas transport unit.

The drawing shows a schematic diagram of a device for implementing the method of the production of methanol for gas production: borehole or "Bush" wells natural gas - 1 train - 2, installation of complex gas is underwater gas and oxygen volume concentration of not more than 1.5% vol. - 5, a cylindrical tube opposite, transverse and coaxial oxygen with a flow rate of Q1in natural gas - 6, a cylindrical tube for turbulent mixing of natural gas with oxygen flow Q17, the compressor oxygen-containing gas (including air) - 8, a reactor with a cylindrical body and two cylindrical reaction zone 9, the set of cylindrical tubes of the first reaction zone 10, the porous filler of the first reaction zone 11, the mixer gas mixture from the first reaction zone and the oxygen volume concentration of from 2 to 12% vol. - 12, a cylindrical tube opposite, transverse and coaxial oxygen with a flow rate of Q2in natural gas with the reaction mixture from the first reaction zone 13, a cylindrical tube for turbulent mixing of natural gas with the reaction mixture from the first reaction zone with a stream of oxygen Q214, the porous filler of the second reaction zone with separated layers - 15.1, 15.2, 15.3, the output gas stream from the second reaction zone 16, recuperative heat exchanger, the cooled natural gas stream QPG, - 17, the cooling gas flow - condenser - 18, a gas separator for vysokoeffektivnaya - 21, metroprolol from the installation of the integrated gas supply to the cable 22, the capacity of the installation of complex gas to collect rectified methanol with a concentration of from 75 to 95% - 23. Regulating and shut-off valves - (B1-B9). The first reaction zone comprising a cylindrical pipe 10 and the filler 11, - I; the second reaction zone, comprising a cylindrical reactor vessel 9 and the outer surface of the cylindrical pipe 10 and the layers of filler 15.1, 15.2 and 15.3, - II; natural gas consumption - QPGthe amount of oxygen volume concentration of not more than 1.5% vol. - Q1the amount of oxygen volume concentration of from 2 to 12% vol. - Q2.

The method is as follows.

Natural gas from a well or well cluster 1 serves to train 2 to unit 3 for gas transport by the standard method [2]. For the production of methanol for gas production and the preparation of natural gas to the transport select it from the train or unit with volumetric rate of QPGand served through the recuperative heat exchanger 17 in the heater 4, which is heated to a temperature of 300-500oC. the Heated gas stream is mixed in the mixer 5 with a stream of oxygen-containing gas from the compressor 8, including air, with a flow rate of Q1when the tion of gases occurs when the turbulent mixing of the jets, fed to the mixer through a comb of cylindrical tubes 6 (oxygen) and 7 (natural gas). The pressure of the gases at the inlet of the reactor 9 range from 10 to 100 ATM. The reactor gas-phase oxidation of methane to methanol consists of two reaction zones. In zone I the gas flow moves within a set of parallel cylindrical tubes 10 with a porous filler 11. As the filler used, for example, bulbs and/or tubes of Pyrex, Teflon, silicon carbide and aluminum oxide.

The first reaction zone is used for the first stage of oxidation of methane in the process of launching a branched chain reaction with subsequent formation of the desired product with high selectivity to methanol (60 wt.%) at small concentrations of formaldehyde, water and products of deep oxidation of methane (CO, CO2H2) due to the use of low oxygen concentration and homogeneous, turbulent mixing of gases with simultaneous heating to the reaction temperature 370-470oWith in porous filler 11 when the Reynolds number Re=100-10000, preferably at 1000-5000. The speed of motion of the gas in the reaction zone is chosen such that the time of diffusion of the molecules of natural gas to the developed surface of the porous filler was mangoletsi diffusion in porous filler assess the range of pore sizes filler D=(0.01 to 10)L, preferably of 0.1-1)L. the Value of= 0,01-0,05. Out of the zone 1 gas stream are mixed in the mixer 12 with a stream of oxygen-containing gas with a flow rate of2with a volume concentration of from 2 to 12% at a pressure and a temperature of 10-100 ATM and 40-50oC. Gases for mixing are fed through the dies of the cylindrical tube 13 (oxygen) and 14 (reaction mixture). Next perenesena a mixture of gases moving in the second zone with filler 15.1 - 15.3 D=(0.01 to 10)L, preferably of 0.1-1)L at Re=100-10000, preferably at 1000-5000. The value of=0,01-0,05. The number of layers of porous filler will vary depending on the volumetric flow rate of natural gas and, accordingly, the size of the reactor. The speed of motion of the gas in this reaction zone is chosen such that the time of diffusion of the molecules of natural gas to the developed surface of the porous filler in each layer was less time of the gas flowing through the layer of filler. The direction of flow of the gas flows in the reaction zones create the opposite and between them provide continuous heat to create kvazistaticheskikh conditions exothermic gasoven is one peremeshennoi mixture of gases due to turbulent flow of the gas stream through the layers of filler with simultaneous alignment of the temperature profile in the reaction zone increases the concentration of oxygen up to 12% vol. in the second reaction zone and, accordingly, the degree of conversion of methane to 10 vol.% in a single pass reactor (without recirculation gas) at a sufficiently high selectivity of the target product (>60 wt.%) at the exit of the reactor, as well as to reduce the concentration of by-products of the oxidation of formaldehyde, water, hydrogen and oxides of carbon).

The presence of instabilities on the selectivity of the target product and the degree of methane conversion in the technology of gas-phase production of methanol is unacceptable in its industrial use [3,5]. The use of porous filler reduces experimentally observed instability of the production of methanol, due, in particular, vibrational modes and large scale turbulence in the reaction zone. This not only expands the possibilities of commercial use of the developed method, but also allows you to increase (compared to the prototype) the selectivity of target product yield and the degree of methane conversion.

The reaction mixture to a temperature of about 350oWith the output from the reactor is passed through tube space recuperative heat exchanger 17 with a sharp fall in its temperature not less than 150-200oC. Simultaneously, the heat exchanger serves natural gas from train 2 or unit 3. Cooling is carried out by heat exchange between the reaction mixture and natural gas in the annular space. In the raise the temperature of the natures is to eliminate the possible decomposition of hot vaporous methanol on the inner surface of metal pipes.

For continuous gas production it is necessary to have an additional supply of methanol for 30 to 40 days of continuous operation in case of emergency situations (a sharp increase of moisture content, significant temperature changes and significant emissions of water in the form of a droplet of liquid, failure of the system to produce methanol and other). Therefore, after the heat exchanger 17 is provided for separating the gas stream into two. One of the threads with the target product guide for metroprolol 21 in the unit for the preparation of gas to transport and/or further metroprolol 22 in the loop 2 to eliminate the possible formation of gas hydrates in gas production [2]. Another thread is subjected to cooling in air refrigerator-condenser 18 with subsequent efficient capture of drops formed in the separator 19. Before serving gas-liquid mixture from the condenser to the separator her acid impurities (mainly formic acid are neutralized. After the separator collected fluid rectificatum in the column 20 and purified (up to 75-95 wt.%) the methanol is collected in the accumulation tank 23 for later use on the unit and/or feed in the loop.

An example of the method.

Speed �https://img.russianpatents.com/chr/8226.gif">10-4the poise of the density of the gas in the reaction zone () - 21,6 kg/m3The characteristic pore size of the porous filler (D) - 0.3 cm, the degree of turbulence () - 0.03 Reynolds Number in the reaction zones (Re) - 1880 thickness of the layer of porous filler in the area of I - 15 cm Thick layer of porous filler in zone II - 15 cm Number of layers of porous filler in zone II - 2
The porous material of the filler - Balls Pyrex
The gas pressure in the reaction zones and 75 ATM
Temperature - 400oWith
The volumetric consumption of natural gas (QPG) - 1700 nm3/h
The volume flow of oxygen in zone I (Q1) to 25.5 nm3/h
The volume flow of oxygen in zone II (Q2) - 200 nm3/h
The degree of conversion of the oxygen in the zone II - 95 vol.%
The degree of conversion of methane in a two-zone reactor - 9,5% vol.
The average reaction time - 2,3
Output at 1000 nm3missed gas
Methanol product - 49,5 kg/1000 nm3
Methanol - 32 kg/1000 nm3
Performance methanol - 55 kg/h
The average composition of the methanol product raw wt.%:
Methanol - 65
Formaldehyde - 6
Water - 28
Formic acid - 0,3
Other (ethanol, propanol, acetone, and so on) - 0,7
the production can increase by 20-40% selectivity yield of methanol by gas-phase oxidation of methane with a higher degree of conversion (up to 10 vol.%) in a single pass reactor. The prototype of the degree of conversion of methane does not exceed (5-6%), and the selectivity of the output of methanol is less than 50 wt.%. In addition, due to continuous developments and create a stockpile of methanol to unit concentration from 75 to 95 wt.% this method allows you to ensure the continuity of its supply to unit and/or train for besidethe mode gas production [2].


Claims

1. A method of producing methanol, comprising separate feeding into the mixer first reaction zone of the reactor purged from drops and solid dispersion of pollution of natural gas under the pressure of 10-100 ATM, preheated to a temperature of 300-500oWith, and oxygen-containing gas, including air, under pressure of 10-100 atmospheres and at a temperature of 40-50oWith that turbulent mixing of the gases in the mixer first reaction zone and the oxidation for a time of 0.2 to 10 s at a temperature of 370-470oC and the oxygen concentration is not more than 1.5. %, with subsequent turbulent mixing of the gases in the mixer of the second reaction zone of the reactor and oxidation in her oxygen-containing gas supplied to the mixer of the second reaction zone for a time of 0.2 to 10 s at a temperature of 370-470oWith that in doing so od is for mixers both reaction zones, subsequent cooling of the reaction mass, after leaving the second reaction zone of the reactor, in the regenerative heat exchanger natural gas, flue gas, characterized in that the oxidation in the first and second reaction zones is performed at a pressure of 10-100 bar, passing the gas stream through an inert porous filler placed in the reaction zone, and the concentration of oxygen in the second reaction zone of about 2-12. % time passing gas through an inert porous filler exceeds the time of diffusion of the reaction products to its well-developed inner surface, while the gas flows in the reaction zones create a counter-current relative to the direction of their flow, while providing a continuous heat transfer through the walls of their side surfaces.

2. The method according to p. 1, characterized in that turbulent mixing and simultaneous heating of the gases to the reaction temperature, passing through the porous filler in the first and second reaction zones is carried out at a Reynolds number equal to Re=VD/2= 100-10000, preferably at 1000-5000, with a characteristic pore size of the filler is D= (0.01 to 10)L, preferred>/img>is the density, dynamic viscosity and the degree of turbulence of the gas stream in the reaction zones, respectively, and the linear flow velocity is determined from the equation V= Q/S, where V is the linear velocity, Q is the volume flow of the gas stream in the reaction zone, L and S, respectively, the thickness of the layer and the front along the geometric flow area of the porous filler.

3. The method according to p. 1, wherein the porous filler in the second reaction zone is placed in layers in the direction of gas flow.

4. The method according to p. 1, characterized in that the produce hardening of the target product at the outlet of the second reaction zone by lowering the temperature of the reaction mixture not less than 150-200oWith regenerative heat exchanger, the cooled natural gas stream from the installation of complex gas or train.

5. The method according to p. 1, characterized in that the exhaust gases leaving the recuperative heat exchanger is divided into two streams, one of which serves together with the target product in the installation of a comprehensive training and, if necessary, it serves in the loop gas field, and from another thread taken methanol by cooling and condensation, with subsequent raketherake gas for later use.

 

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SUBSTANCE: invention relates to catalytic oxidation of saturated hydrocarbons with oxygen-containing gas. Process according to invention comprises contacting alkane with oxygen source in presence of catalyst including compound of general formula: , where R1 and R2 independently represent hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxy, alkoxy, carboxyl, alkoxycarbonyl, or acyl, or R1 and R2 can together form double bond or aromatic or non-aromatic ring; Y represents oxygen atom; X oxygen atom to hydroxyl group; m is integer 1 or 2; and n = 1. Process is conducted at 20 to 100°C. Advantageously, catalyst includes cocatalyst.

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EFFECT: invention enables to obtain the end product using an efficient and cheap method without using a catalyst.

34 cl, 2 ex, 36 dwg

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1 ex, 1 dwg

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FIELD: chemistry.

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