Continuous production method for methanol

Abstract

The present invention relates to a method for producing methanol from hydrogen and carbon monoxide, both in the gaseous state, in which hydrogen and carbon monoxide are contacted with a liquid in at least one bubble or loop or jet loop reactor, the liquid comprising at least one solvent, an alcohol and / or an amine as nucleophilic promoter, optionally an additional base, and a catalyst, the catalyst comprising a transition metal and at least one Lewis basic ligand. At least one device is provided for removing heat from the reactor. The methanol formed as product is then separated by at least one phase separation device.

Description

【Technical Field】 【0001】 The present invention relates to a method for producing methanol from hydrogen and carbon monoxide both in gaseous state. In particular, the present invention relates to the use of a suitable reactor and the separation of process products. 【Background Art】 【0002】 <General> Methanol, also known as methyl alcohol, is an organic compound with the molecular formula CH3OH. Methanol has a current annual production of approximately 100 million tons and is one of the most widely produced organic chemicals. This is because methanol is an important starting material for the basic products of aldehydes, formic acid, and acetic acid in particular. Furthermore, methanol and its derivatives are used as energy sources, and in particular, methane is formed therefrom. Furthermore, methanol is required for the synthesis of biodiesel and the antiknock agent MTBE. Methanol can also play a role in the seasonal storage of electrical energy. For example, this is done through direct reconversion to electricity using a fuel cell (direct methanol fuel cell) or indirect reconversion (H2 reformer), or combustion in a suitably adapted turbine. Finally, methanol has a high volumetric energy density and weight energy density, and methanol can be easily transported, so it will be particularly important in the future for all distributed variable energy generation processes that are influenced by weather conditions, namely solar power generation and wind power generation. 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0003】 <Explanation of the Problems and Conventional Basic Technical Implementations> Currently, industrial methanol production is mainly carried out using heterogeneous catalysts, primarily on solid catalysts, mainly copper-zinc-aluminum oxides, with gaseous reactants carbon monoxide (CO) and hydrogen (H2). The main drawback of these heterogeneous catalysts for producing methanol from synthesis gas is the high temperature and pressure required. The conversion of carbon monoxide and hydrogen to methanol has a standard enthalpy of -90.6 kJ / mol, meaning that the higher the temperature, the greater the equilibrium shifts toward the starting compounds (carbon monoxide and hydrogen). Heterogeneous catalysts require high activation energy and, consequently, high temperatures, which reduces the proportion of product in the reaction equilibrium. Therefore, high pressure is necessary to shift the equilibrium toward the product side. Despite these measures, the typical yield per operating cycle is only about 6-15 wt%, and unreacted CO and H2 must be recycled at considerable cost. The compression of reactants and recompression of unused gases make this type of production process energy-intensive, resulting in a high proportion of OPEX in the methanol production cost. In addition to the high exothermic rate of the reaction itself, this type of transformation requires high temperatures, necessitating intensive cooling of the reactor, particularly the catalyst. Due to the nature of this approach using gaseous reactants and a solid catalyst, a considerable amount of heat is released in the catalyst, whose optimal performance is guaranteed only in the low-temperature range. 【0004】 Conventional industrial manufacturing methods are related to the fundamental properties of copper-zinc-aluminum oxide catalysts, and the efficient coupling of plant components, as well as the flow of materials and energy, is also related to the fundamental properties of this catalyst. However, the economic efficiency of industrial processes is always greatly influenced by two factors: one is the thermodynamics of the equilibrium (CO + 2H2 ⇔ CH3OH) based on the reactants and products, and the other is the activation barrier based on the catalytic approach. The so-called low-pressure method, using heterogeneous catalysts, can now be implemented on a large scale with similarly good yields, but this method still uses temperatures exceeding 200°C and pressures of 50-100 bar. This high load on plant components and materials also results in high investment costs and increases the proportion of CAPEX in the price of methanol production. [Means for solving the problem] 【0005】 <Principle of the Invention> Therefore, the fundamental advantage underlying the method according to the present invention is that the novel catalytic process can be carried out at a remarkably low temperature, for example, 150°C, and at a considerably low pressure, for example, 50 bar. 【0006】 The industrial method for producing methanol described herein represents a particularly economical and environmentally friendly conversion of CO and H2 to methanol, based on a novel catalytic approach with specific technical means. 【0007】 The first characteristic of the specific technical implementation is, in essence, the implementation of a novel catalytic approach in a gas-liquid system, which differs from previously known methods in that the reaction mainly takes place in the liquid phase. Preferably, the catalytic action is carried out as a homogeneous catalytic system in which the catalyst is dissolved in a solvent, or an immobilized catalyst is used, and the synthesis gas is converted to methanol according to the novel approach. 【0008】 The advantage of a liquid phase containing a homogeneous or immobilized catalyst is that the released heat can be directly absorbed and dissipated, and unlike conventional methods, localized temperature increases do not irreversibly alter the catalyst, thereby rendering it inactive, and / or create so-called hot spots where higher local temperatures lead to undesirable side reactions, resulting in the loss of reactants without an increase in product. By using a liquid phase, it is necessary to introduce the gaseous reactants H2 and CO as intensively as possible. Most industrial gas-liquid reactors are based on stirred tanks or bubble tower reactors with gas introduction (directly into the liquid or via a stirrer). 【0009】 Bubble tower reactors are the least expensive form of gas-liquid reactor, which is why they are the most frequently used. In addition to these typical gas-liquid reactors, loop reactors are also used as a niche application. Typical loop reactors include jet zone loop reactors, impacting jet reactors, loop venturi reactors (bath loop reactors), jet loop reactors, and jet nozzle circulation reactors (jet loop reactors). This is used particularly in the form of jet loops (jet loop reactors) in hydroformylation (homogeneous catalyst, CO + H2 + olefin → aldehyde) and biocatalytic oxidation (enzymes, substrate + O2 → oxidation product). This type of reactor has been used when the reaction rate is very fast, such as in hydroformylation and enzyme catalysis. Therefore, the usual gas supply to the liquid in a bubble tower reactor has a limiting effect, and thus the reaction rate is determined by the material transfer rate. Conversely, bubble tower reactors are typically used when the reaction rate is slow. 【0010】 The second characteristic is that the reaction is carried out in a gas-liquid manner, particularly in a loop reactor. However, this type of reactor is not initially obvious, as the reaction on which the present invention is based using previously known catalysts does not have a reaction rate as fast as hydroformylation or enzyme catalysis. Nevertheless, the methanol synthesis described herein is characterized by the absence of the metered addition of any additional substrates (other than H2 and CO). This has a major drawback, unlike when other components are added, as the reaction solution is not continuously cooled by the exothermic reaction. Therefore, the strongly exothermic reaction of methanol synthesis results in strong heating throughout the reaction process. However, catalysts, especially homogeneous catalysts, have a specific temperature range in which they catalyze the desired reaction with high selectivity. Therefore, methanol synthesis requires intensive cooling. 【0011】 The use of loop reactors results in better mixing of gas and liquid and better heat distribution compared to other gas-liquid reactors. Heat can be removed by internal or external heat exchangers. Internal heat exchangers are either directly immersed in the reaction solution (e.g., cooling coils, U-tubes, heat exchanger plates), or the reactor wall transfers heat to the heat exchanger. If the reaction solution is circulated in a circulation path, heat can also be dissipated through a heat exchanger in this external circulation path. The catalyst systems described so far are not fast enough for loop reactors, but the absence of continuous metering and addition of co-substrates (except CO and H2), combined with the important situation of heat removal, makes this type of reactor particularly promising for industrial implementation. 【0012】 A third feature of this methanol synthesis, particularly for economical implementation, is the use of one or more reactors and one or more external heat exchangers. Therefore, the optimal combination of individual components can be selected depending on the scale of the production plant. 【0013】 The fourth feature is addressing the most economical separation of the generated methanol. This can be done in several sequential steps based on the simple principle of phase separation. For example, not only a gas-liquid system but also gas-liquid-liquid subgroups can be used, which are characterized by the presence of multiple liquid phases, for example, one phase being catalyst-rich and another phase being product-rich. By separating or successively removing the product-rich phase, the total flow rate for separating methanol is reduced. Methanol is then removed from the product-rich phase. This can be done by using a methanol-selective membrane (e.g., nanofiltration), or by simple distillation (flash evaporation) or multi-stage distillation (column). 【0014】 Preferably, this method is carried out using some of the features of both independent claims 1 and 6. 【0015】 In this method, the reactants hydrogen (H2) and gaseous carbon monoxide (CO), which are in a gaseous state, are converted to methanol. The reaction takes place in a liquid. This liquid comprises at least one solvent, an alcohol and / or amine as a nucleophile promoter, and a catalyst. This catalyst may exist in liquid form or as a solid in the liquid. The catalyst itself comprises at least one Lewis basic ligand (e.g., N / NH, O / OH, S / SH, C / CH, Si / Si-H, B / BH) and a transition metal. It is a metal catalyst having the basic structure M-LB, where M is a metal ion and LB is the center of at least one Lewis base. In its simplest form, the catalyst is M shown in the following structural formula (1) x N y It can be written as (x=1~4, y=1~2). 【0016】 [ka] 【0017】 Simple examples are manganese nitride or iron nitride. In addition to artificial manganese nitride, natural minerals such as siderazote (Fe3N) and lowerite (Fe4N), which are iron nitrides, are also known. 【0018】 Furthermore, the organometallic complex shown in Structural Formula (2) is well-suited, where M is a metal ion and LB is the center of at least one Lewis base. In this variant form, LB contains at least one atom selected from the group consisting of N, P, O, S, or C. 【0019】 【Chemical formula】 【0020】 The transition metal is an ion selected from the group consisting of manganese, rhenium, iron, ruthenium, chromium, molybdenum, tungsten, cobalt, rhodium, iridium, nickel, copper, palladium, and platinum. In particular, manganese, iron, ruthenium, or molybdenum have good properties. Especially, the use of manganese, ruthenium, or molybdenum as the central ion shows a high conversion rate (TON). 【0021】 Typical homogeneous catalysts include the following. 【0022】 【Chemical formula】 【0023】 This reaction is preferably carried out in the presence of a base. In particular, it has been found that an alcoholate can promote the base. Suitable bases include phosphates, sulfates, carbonates, or alcoholates of lithium, sodium, potassium, or calcium. For example, the use of K3PO4 or KOMe has been successful. 【0024】 This reaction can preferably be carried out in a bubble column, loop reactor, or jet-loop reactor. Such reactor types are known from the continuous reaction of a gas with at least one liquid. For example, International Publication No. 2010 / 923018 describes a method for converting compounds having olefin double bonds to aldehydes and / or alcohols using synthesis gas. 【0025】 A loop reactor consists of a tubular reactor and a material recirculation system. This makes it possible to achieve reaction control with characteristics intermediate between a tubular reactor and an ideal mixed-and-stirred-tank reactor. In its basic function, the gas mixture flows into the reactor, for example, from above or below, resulting in the formation of a column of bubbles in the inner tube of the loop reactor. In addition to this actual tubular reactor, there is a material recirculation system that allows the reaction volume and residence time in the bubble reactor to be individually adjusted based on the rate of material flow being recirculated. Therefore, in a loop reactor, spatial separation between the upward and downward flow directions is important. 【0026】 Therefore, a loop reactor is a special type of bubble reactor in which a rising liquid containing gas is circulated in a defined manner by a coaxial guide tube structure. There are several types of loop reactors. In the simplest case, the gas is introduced into the guide tube through a central nozzle at the bottom of the reactor. The bubbles carry the liquid upward according to the principle of an air-lift pump. The liquid flows backward downward, degassing as it passes over the upper edge between the reactor shell and the guide tube. Gas dispersion can be significantly improved by adding propulsion jets. 【0027】 There are two basic types of loop reactors, distinguished by an external loop where spatial separation is clearly visible. In this type, an upward-flow column and a downward-flow column are arranged side-by-side as a cylinder, connected at the top and bottom by tubing. Loop reactors with an internal loop have a smaller cylinder in the center of a larger diameter cylinder. The connection between the two cylinders is made possible by making the ends of the smaller cylinder, which functions as a bubble reactor, slightly shorter than the surrounding cylinder. This design is space-saving and is therefore used, especially for larger dimensions. 【0028】 So-called jet loop reactors, or jet nozzle reactors, are characterized by a uniform distribution of gas and liquid. In a jet loop reactor, the liquid is supplied to the bottom of the reactor in a jet stream so that the gas can be captured and the gas flow can be split. 【0029】 In an impactor jet reactor, at least two separate circulating flows are generated by multiple nozzles and directed toward each other. This configuration results in a high specific power input in the impaction zone, which has a large mass exchange capacity. The drawback is that the structure becomes more complex. 【0030】 In the case of so-called down-flow loop reactors, a very long gas residence time is characteristic, which allows the overall height to be set low. 【0031】 Loop reactors are used in many technical gas-liquid reactions. However, the focus here is on the reaction of liquid reactants with gaseous reactants. In this case, however, the liquid reaction environment is provided by the solvent, where the reaction products are also liquid, and the two reactants, hydrogen and carbon monoxide, exist in gaseous form. Therefore, it is not common to use loop reactors for continuous reactions of gaseous reactants. 【0032】 Furthermore, since the reaction is a very exothermic reaction in this application, it is preferable that such a reactor has at least one device for heat dissipation. 【0033】 This makes it possible to produce methanol at much lower pressures, and therefore significantly reduce the costs of CAPEX and OPEX. 【0034】 Furthermore, it has been found to be advantageous to use at least two loop reactors or jet loop reactors connected in parallel and / or in series. This is because, in the case of parallel connection, individual plant components can be made smaller in size, while in the case of series connection, the degree of conversion of each can be controlled by the corresponding catalyst concentration, thus avoiding localized temperature stress due to strong exothermic reactions. 【0035】 Regarding at least one heat dissipation device, it has been found advantageous to install the heat dissipation device either directly inside the reactor or on the outside of the reactor in order to achieve the most uniform temperature control possible within the reactor. However, in principle, it is also conceivable to design the device so that the flow of product discharged from the reactor is cooled. This simplifies the design. 【0036】 Similarly, such a heat dissipation device could be incorporated into the aforementioned circulation of at least one reactor, i.e., the recirculation of the liquid, thereby cooling the liquid again before it comes into contact with the reactants, hydrogen and oxygen, once more. Depending on the design of the loop reactor, this heat dissipation device could be located inside or outside the reactor shell. 【0037】 Furthermore, when the reactors are arranged as a jet loop bundle reactor, this is advantageous because it facilitates cooling between individual reactors and thus allows for parallel reaction control within individual bubble columns in a single apparatus. This also leads to a more uniform temperature profile. 【0038】 Alternatively, the present invention also provides a method for producing methanol from gaseous hydrogen and gaseous carbon monoxide, comprising contacting hydrogen and carbon monoxide with a liquid in at least one reactor. The liquid comprises at least one solvent, an alcohol or amine as a nucleophile promoter, and a catalyst. The catalyst comprises a transition metal and at least one Lewis basic ligand. After the reaction has occurred, the formed methanol is present in the liquid phase, which is transferred to a container after the reaction, where a liquid phase and a gas phase are formed. The formation of these phases can optionally be supported by a pressure reduction of 5% to 90%, preferably 10% to 60%, particularly preferably 20% to 50%, or by a reduction to an absolute pressure of 1 to 20 bar, preferably 5 to 10 bar. Optionally, as a supplement or alternative to the pressure reduction, the temperature may be reduced by cooling by at least 5%, preferably at least 20%, particularly preferably at least 50%. 【0039】 The resulting product-rich phase contains at least 55% by weight, preferably at least 70% by weight, and particularly preferably at least 90% by weight of the desired reaction product methanol, based on the total liquid phase discharged from the reactor, while the solvent is present in the liquid phase at least 55% by weight, preferably at least 70% by weight, and particularly preferably at least 90% by weight. This makes the separation of the product from the solvent very easy. 【0040】 It has been found to be particularly advantageous to recirculate the liquid phase to at least one of at least one reactor. Thus, on the one hand, the liquid containing all components, especially the catalyst, is actually completely recirculated, and on the other hand, the methanol contained therein can be recirculated again and separated again accordingly, resulting in no loss of product. 【0041】 Furthermore, it has been found advantageous that the apparatus is connected downstream of the reactor and positioned so that the liquid phase removed from the reactor first passes through the apparatus before entering the container. Using this apparatus, unreacted hydrogen and / or carbon monoxide can be separated from the liquid phase by simple phase separation. This can be facilitated by slightly reducing the pressure of the system, particularly by lowering the pressure by 1 to 5 bar, and / or slightly lowering the temperature, for example, by 10 to 25°C, preferably 25 to 50°C. This enables phase separation and, at the same time, allows for recirculation into the system. 【0042】 Furthermore, it has been found to be advantageous that the hydrogen and / or carbon monoxide separated from this apparatus are returned to at least one of the at least one reactors. In this way, the loss of reactants can be avoided, and the overall efficiency of the process can be increased. 【0043】 Regardless of the reactor selection and purification type, it was found to be advantageous if the alcohol and / or amine used as an accelerator in the liquid originated from the group comprising methanol, glycol, pyrrole, indole, aniline, and derivatives of one of these compounds. 【0044】 In addition, or alternatively, it has been found that it is advantageous for the alcohol and / or amine to have a linear, branched, or cyclic structure as an accelerator. All embodiments result in particularly high conversion rates. 【0045】 Furthermore, it has been found to be advantageous when the catalyst itself is only an indirect component of the liquid, that is, when the catalyst does not exist in liquid form but is immobilized, i.e., bonded to a solid surface. This facilitates, for example, catalyst replacement. This solid may be, for example, a sparingly soluble oxide, silicate, or polymer. 【0046】 Conversely, homogeneous catalysts have the advantage that the reaction is virtually completely independent of mass transfer phenomena. 【0047】 Furthermore, in the case of product separation by methanol evaporation, it was found to be preferable to use at least one aliphatic solvent having a higher boiling point than methanol, because this allows for the separation of solvent residues in the resulting methanol by simple distillation. 【0048】 Nanofiltration is particularly suitable for product separation using membrane technology. In this case, care must be taken to ensure that all components other than methanol used are clearly different from methanol in molar mass. The catalyst, accelerator, solvent, and, if necessary, the base should be significantly larger and broader than methanol. 【0049】 In a more preferred embodiment, the reactor temperature is set to 20-180°C, preferably 50-170°C, and particularly preferably 80-150°C. This is because good conversion rates can be achieved at these reaction temperatures without damaging the catalyst. Pressures of 1-100 bar, preferably 5-80 bar, and particularly preferably 10-50 bar have been found to be advantageous. This allows for a significant reduction in the overall load on the apparatus system compared to methanol synthesis using conventional heterogeneous catalysts, in any combination of the aforementioned temperature and pressure ranges. 【0050】 Finally, this method can be carried out continuously or semi-continuously, which facilitates large-scale applications. In particular, when the method is carried out continuously, it can be controlled in an open-loop or closed-loop manner using the outflow of the liquid phase from the reactor and / or the inflow of hydrogen and / or carbon monoxide into the reactor. 【0051】 Further advantages and possible embodiments of the present invention are evident from the drawings and their description, and each feature is disclosed individually and in any combination. [Brief explanation of the drawing] 【0052】 [Figure 1] Figure 1 shows a basic design of a reactor. [Figure 2] Figure 2 shows the reactors connected in parallel. [Figure 3] Figure 3 shows another basic design for the reactor. [Figure 4] Figure 4 shows a basic reactor design combined with a single-stage process. [Figure 5] Figure 5 shows a basic reactor design combined with a two-stage process. [Modes for carrying out the invention] 【0053】 Figure 1 shows a basic design using a loop reactor. The heat exchange medium is introduced into reactor 110 via line 131. The heat exchange medium is then removed again via line 132. 【0054】 This reactor contains a liquid comprising a solvent, an alcohol and / or an amine, at least one nucleophilic accelerator, and a catalyst. A gas is also injected into reactor 110 via line 121. This gas is a so-called synthesis gas mixture consisting of hydrogen and carbon monoxide. 【0055】 The product flow is drawn from the reactor 110 via line 122 by pump 123. Part of this flow is sent to the processing unit via line 126, while the other part is cooled by passing through heat exchanger 125 and then returned to the reactor 110 via line 124. Line 124 may also be used to install a device for product separation. This may be, for example, a nanofiltration system capable of continuously removing methanol from the system. Optionally, a gas separation section for unused carbon monoxide and hydrogen may be provided upstream of the product separation device. This allows for the release of gases that were not converted during methanol separation. 【0056】 Figure 2 shows an example of a parallel connection of three loop reactors 210a, 210b, and 210c. Here again, the heat exchange medium is supplied through line 231. The individual supply lines are referred to as a, b, and c, corresponding to the reactors. Similarly, the heat exchange medium is discharged again through line 232, which includes individual discharge lines 232a, 232b, and 232c. 【0057】 The necessary reaction gases, hydrogen and carbon monoxide, are introduced into reactors 210a, 210b, and 210c via line 221, which includes inlet lines 221a, 221b, and 221c. The product flow is removed by pump 223 from the individual reactors 210a, 210b, and 210c via lines 222a, 222b, 222c, and 222. A portion of this flow is supplied to an apparatus (not shown) via line 226. The remainder of this flow is cooled in heat exchanger 225 and returned to the reactors via line 224, which includes associated lines 224a, 224b, and 224c. 【0058】 Additionally, a device for product separation can be installed in line 324. This may be, for example, a nanofiltration system capable of continuously removing methanol from the system. Optionally, a gas separation unit for unused carbon monoxide and hydrogen can be installed upstream of the product separation device. This allows unconverted gases to escape during methanol separation. 【0059】 Figure 3 shows an example of separating and removing the recirculation flow from the discharge flow. For this purpose, the gaseous reactants are supplied via line 321, and the portion removed from the circulation path is discharged via line 326. The remaining portion is pumped by pump 323 through line 322 and recirculated through heat exchanger 325 to the associated line 324. The heat exchange medium enters reactor 310 via line 331 and is removed again via line 332. 【0060】 Figure 4 shows some possible processes. While it is shown in combination with a loop reactor, it should be emphasized that this type of process is possible with any other type of reactor, as shown in Figure 5. 【0061】 The heat exchange medium is introduced via line 421 and withdrawn again via line 432. Hydrogen and carbon monoxide are introduced in gaseous form via line 421 into a reactor 410 filled with the liquid according to the present invention and withdrawn via line 422 by pump 423. A portion of the flow thus withdrawn is resupplied to the reactor 410 via line 424 and the associated heat exchanger 425. 【0062】 The discharged partial flow 426 is supplied to the apparatus 440, where it is separated into a liquid phase and a gas phase. This can be done by pure phase separation. If necessary, this is carried out by reducing the pressure of the system by, for example, 10-80%, preferably 20-60%, and preferably to an absolute value of 5-10 bar. Preferably, a temperature reduction of 1-50% may be performed additionally or alternatively. 【0063】 The gas phase, containing the main portion of the methanol fraction, is withdrawn via line 444. The liquid phase is returned to reactor 410 via line 441 by pump 442. Mixing can be performed in the form shown by mixing the flows from lines 421 and 441, or via separate introductions to the reactor. Cooling in circulation line 441 is possible by at least one heat exchanger (not shown). 【0064】 Finally, Figure 5 shows a more complex processing system, in which the use of a loop reactor with supply of heat exchange medium via line 531 and withdrawal of heat exchange medium via line 532 is only optional. 【0065】 Hydrogen and carbon monoxide, as gaseous reactants, are introduced into reactor 510 via line 521 and withdrawn via line 522 by pump 523. Partial recirculation to reactor 510 occurs via line 524 and a heat exchanger 525 located in that line. The portion of the flow from line 522 that is not recirculated via line 524 is supplied to apparatus 550 via line 526. In apparatus 550, the liquid and gas phases are separated. This can be done solely by phase separation. If necessary, this is accomplished by slightly reducing the pressure of the system, for example by 1% to 5%, preferably up to 5 bar. Additionally or alternatively, a temperature reduction of preferably 1% to 5% is also possible. 【0066】 The gas phase is returned to the reactor via line 552 by pump 553. The resulting liquid phase is supplied to container 540 via line 551 for further purification of the methanol it contains. Here, the second phase is separated as described with respect to Figure 4. 【0067】 From vessel 540, the liquid phase is returned to reactor 510 directly or indirectly via line 542 through pump 543. Further cooling is possible by a heat exchanger (not shown). The gas phase separated in vessel 540 is supplied via line 541 for possible further methanol purification. This methanol purification may be nanofiltration and / or distillation by means of (not shown). 【0068】 <Examples> The 10L jet loop reactor has a combined heating-cooling primary circulation path and a secondary circulation path designed solely for cooling. 【0069】 2.48 g of Mn(I)-PNP catalyst (CAS1919884-90-4) (structural formula below) [ka] In addition, 8.77 g of potassium methanolate (KOMe) was added as a base and dissolved in 500 mL of 1-octanol at 50°C. This alcohol also functions as an accelerator, or methanol can be used. A total of 5.0 L of 1-octanol was used as the solvent. 【0070】 In a semi-continuous (semi-batch) operation, 104.5 NL / min of hydrogen and 49.8 NL / min of carbon monoxide were introduced at a pressure of 25 bar and an average temperature of 120°C. The main part of the reaction occurred within 1 hour from approximately 110°C and 25 bar. Under these experimental conditions, a turnover number (TON) of 208 was measured relative to the amount of catalyst used. [Explanation of symbols] 【0071】 110... Reactor 121, 122… lines 123... Pump 124... Line 125...Heat exchanger 126~128…Line 131, 132… lines 210a, 210b, 210c… Reactors 221, 122… lines 223... Pump 224... Line 225...Heat exchanger 226~228…Line 231, 232… lines 310... Reactor 321, 322… lines 323... Pump 324... Line 325…Heat exchanger 326~328…Line 410… Reactor 421, 422… lines 423... Pump 424... Line 425...Heat exchanger 426, 428… lines 431, 432… lines 440…Phase separation device 441... Line 442... Pump 443... Line 510… Reactor 521, 522… lines 523... Pump 524... Line 525...Heat exchanger 526~528…Line 531, 532… lines 540…Phase separation device 541, 542… lines 543... Pump 543... Line 550…Container 551, 552… lines 553... Pump

Claims

[Claim 1] A method for producing methanol from hydrogen and carbon monoxide, Hydrogen and carbon monoxide, both in a gaseous state, are brought into contact with a liquid in at least one bubble reactor, loop reactor, or jet loop reactor. The liquid comprises at least one solvent, an alcohol and / or amine as a nucleophile enhancer, an optional additional base, and a catalyst. The catalyst comprises a transition metal and at least one Lewis basic ligand. At least one device for removing heat from the reactor is provided. Methanol is formed as a product. method. [Claim 2] In the method according to claim 1, Using at least two bubble reactors and / or loop reactors and / or jet loop reactors connected in parallel and / or in series, method. [Claim 3] In the method according to claim 1, At least one of the devices for removing the heat is located inside the reactor or on the outer shell of the reactor. method. [Claim 4] In the method according to claim 1, At least one of the devices for removing the heat is incorporated into the circulation path of at least one of the reactors. method. [Claim 5] In the method according to claim 1, The reactor is a loop bundle reactor or a jet loop bundle reactor. method. [Claim 6] The method according to Claim 1, The methanol that was formed was in the liquid phase. After the reaction, the liquid phase is transferred to a container to form a liquid phase and a gas phase. The formed methanol is present in the gas phase in an amount of at least 55% by weight, and trace amounts of the solvent, catalyst, nucleophile promoter, and base are present in the liquid phase. method. [Claim 7] In the method according to claim 6, The liquid phase is recirculated from the container to at least one of the at least one reactor. method. [Claim 8] In the method according to claim 6, The separation of unreacted hydrogen and unreacted carbon monoxide from the liquid phase is carried out in the apparatus located downstream of the reactor, before it enters the container. method. [Claim 9] In the method described in claim 8, Hydrogen and / or carbon monoxide are recirculated from the apparatus to at least one of the at least one reactor. method. [Claim 10] In the method according to claim 6, As the alcohol and / or amine used as the accelerator, at least one compound is selected from the group comprising methanol, glycol, pyrrole, indole, aniline, and a derivative of one of the compounds in this group. method. [Claim 11] In the method according to claim 6, The alcohol and / or amine used as accelerators have a linear, branched, or cyclic structure. method. [Claim 12] In the method according to claim 6, The catalyst is present bound to the surface of a solid. method. [Claim 13] In the method according to claim 6, As the at least one of the solvents, an aliphatic solvent having a higher boiling point than methanol is used. method. [Claim 14] In the method according to claim 6, In at least one of the reactors, the temperature is 20 to 180°C and the pressure is 1 to 100 bar. method. [Claim 15] In the method according to claim 6, The method is carried out continuously or semi-continuously. method. [Claim 16] In the method according to claim 1 or 6, The method is carried out continuously, and the method is controlled in an open-loop or closed-loop manner using the outflow of the liquid phase from the reactor and / or the inflow of hydrogen and / or carbon monoxide into the reactor. method.

Images