JPH05504904A - Homogeneous catalyst formulation for methanol production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a novel homogeneous catalyst formulation for methanol production. These new treatments The method has numerous characteristics such as liquid phase performance, low temperature, low pressure performance, high activity, and high selectivity. ■ Over 90% gas loss in a pass, and approximately 97% under optimal conditions Conversion rates can be achieved. Since this catalyst system is a liquid phase system, -carbon oxide and hydrogen This reaction is exothermic and allows the reaction of methanol to form methanol. Therefore, it proceeds under sufficiently isothermal conditions. Conversely, it is used for methanol production. Traditional pelletized solid catalysts form hot spots within the reactor and Pots prevent this process from running efficiently. Furthermore, the catalyst is in a solution state. Therefore, it is possible to decouple the removal of the heat of reaction from the kinetics. Wear. Thus, unlike existing methods, this method allows Designed to optimize heat removal and kinetics for optimal physical and thermal performance It can be incorporated into the manufacturing apparatus separately from the elements of the manufacturing apparatus.

The homogeneous catalyst formulation of the present invention overcomes other deficiencies of known solid phase methanol synthesis catalysts. Also eliminates points. Typically, known methods involve high temperatures (250°C) and high pressures (76°C). 5 psi) and is limited by low equilibrium conversion (60%). Book Using the catalyst of the invention, methanol can be produced at low temperature and pressure, resulting in high equilibrium conversion. It is possible to achieve a

Additionally, known types of catalysts, such as pellet type catalysts, typically have a indicates the gas conversion rate and therefore operates the production equipment at an economically acceptable efficiency. In order to do so, it is necessary to recirculate the feed gas. Therefore, the partial acid of natural gas While oxidation produces an ideal methanol feed gas, partial oxidation It cannot be used to produce feed gas. This is because such a system has a very low This is because it requires the use of a feed gas having an active gas, especially nitrogen gas concentration. Applicable An inert gas, such as nitrogen gas, is added to the recycle stream to maintain process efficiency. should be kept at a low value. Generates a feed gas containing a low concentration of inert gas In order to achieve this, the partial oxidation must be carried out using oxygen, and this method makes the feed gas production method difficult to implement. The catalyst system of the present invention is a feedstock for said synthesis. This makes it possible to use a gas partial oxidation method. This is because its high conversion rate Eliminates the need for recirculating flow, thus allowing the use of air rather than oxygen This makes it possible to save a large amount of cost for oxygen production. ■By pass Another improvement resulting from the high efficiency of the method that allows the operation of Atmospheric nitrogen introduced into the system through a partial oxidation step is and which can be expanded to provide energy for e.g. air compression. The point is that it is possible.

The present invention provides a homogeneous catalyst that provides high gas conversion at low temperatures and pressures. It is possible to produce methanol from a syngas feed containing an inert gas at a do. This makes the reaction conditions and process more efficient than conventional methanol catalysts. This means that it will be significantly improved.

Detailed description of the invention The present invention includes a novel homogeneous catalyst which converts carbon monoxide and hydrogen into methanol. can be used to synthesize. This homogeneous catalyst can be easily produced and is known in the art. It has superior activity compared to methanol catalysts and can be used at low temperatures and pressures in the reactor. ■ Also allows the use of supply gases containing inert gases. and this catalyst provides high gas conversion.

The homogeneous catalyst of the present invention is dissolved in methanol or a mixture of methanol and a cosolvent. Contains two types of ingredients. These two components are a transition metal carbonyl complex and an alkali It is a coxide. The transition metals include copper, nickel, palladium, cobalt, and ruthenium. selected from the group consisting of aluminum, iron, molybdenum and mixtures of these metals. preferred The most common transition metal is nickel.

This two-component catalyst is in the state of methanol solution, and methanol is the methane in the reactor. It can be obtained from the nol product. A co-solvent may also be used, and the co-solvent The medium is preferably an organic oxygen-containing cosolvent that is compatible with methanol. appropriate assistance Solvents include saturated hydrocarbons, amine solvents, ethers, esters, and alkyl polyethers. and hydroxyalkyl polyethers (wherein the carbon chain contains one or more (with an intervening oxy group), and alcohols. As a preferred co-solvent is tetrahydrofuran, 2-methyltetrahydrofuran, octane, and trihydrofuran. toluene, p-dioxane, t-amyl alcohol, t-butyl alcohol, poly Alcohols, glycol derivatives such as polyethylene glycol and triglycol dimethyl ether, dimethyl oxalate and crown of resorcinol Ether can be mentioned.

Since the homogeneous catalyst of the present invention has high activity, -methanol from carbon oxide and hydrogen can be The catalytic production of olefins can be carried out under mild conditions. This catalyst has 20 to 15 Works effectively at temperatures within the range of 0°C, preferably 100-15°C (similar) The effective pressure in the reactor is also 50 to 300 ps, preferably 100 to 150 ps. may be within the range of si.

The feed gas for the production of methanol using the catalyst of the invention is preferably natural gas. Synthesis gas is produced by the partial oxidation of This supply gas is an inert gas, e.g. It can be diluted with nitrogen and methane. This catalyst produces small amounts of hydrogen sulfide, carbon dioxide and Syngas, which can contain water and water, is almost anhydrous and contains no carbon dioxide. It is preferable that

Most homogeneous catalysts rely on the two materials used to prepare the catalyst, namely the transition metal. It is a reaction product between a substance and an alkoxide substance. The transition metal substance is methanol. It is a substance that can generate the corresponding transition metal carbonyl in the reaction mixture. The transition metal substance is It can be a metal carbonyl or carbonyl precursor. The “cal” used here The term Bonyl Precursor J refers to the transition metal precursor that is formed in situ when dissolved in methanol. means a substance that can form rubonyl. The transition metal carbonyl or transition metal carbonyl The rubonyl precursor has a mononuclear shape or a cluster shape. can be used to produce the catalyst of the present invention. Preferred transition metals, namely nickel When using nickel carbonyl in any form, e.g. nickel tetra Carbonyl: N1(Co)4 or the nickel carbonyl in methanol solution Any carbonyl precursor that can be produced can be used to prepare the homogeneous catalyst of the present invention. Ru. Also, mixtures of two transition metal carbonyls or carbonyl precursors, e.g. For example, using a bimetallic system such as a mixture of nickel carbonyl and molybutene carbonyl. It can also be used.

Another aspect of using bimetallic systems is the transition metal carbonyl or carbonyl The precursor, e.g. nickel tetracarbonyl, is Can be used with substances that contribute as alkoxides and also transition metal alkoxides, e.g. For example, copper methoxide can also be used.

The transition metal carbonyl or carbonyl precursor substance has, for example, nitrogen on the surface. To prepare the homogeneous catalyst in the form of any supported species that forms the It can also be blended into a methanol solution. In this way, the homogeneous catalyst is The system can be operated as either homogeneous or heterogeneous by supporting it on a carrier such as light. I can make it work.

The second material used in the preparation of the homogeneous catalyst of the present invention contributes as an alkoxide component. It is a substance that Materials useful as this second reactant include any metal, amine, or or other substances that generate or can form alkoxides in the presence of methanol solvent systems. It is. Possible alkoxide generators include Groups 1A, IIA and IIB metals. an alkoxide, where the alkoxy group is derived from an alcohol having 1 to 6 carbon atoms. Preferably, it is an original group. Preferably, the cation is an alkali metal, an alkali Aliphatic alcoholades such as earth metals or mixtures thereof. more preferable contains sodium, potassium, rubidium, cesium, barium and calcium. most preferably potassium methoxide. Mail An example of an amine that can form an alkoxide in tanol solution is 1,8-diazobisic. ro[5,tO)undec-7-ene and tetramethylammonium methoxide It is.

The substance contributing as the alkoxide is added to the reactor during the preparation of the homogeneous catalyst of the present invention. When the cation or non-alkoxide ion is Adding substances that inactivate and increase the concentration of alkoxide ions in solution is also possible. Complexing and/or coordinating substances or ligands suitable for such purposes Crown ethers, cryptands, and alkali metals and alkaline earths Contains polydentate ligands for similar metals. Preferred complexing and/or coordinating ligands are 2,2-bipyridine, diethylene glycol dimethyl ether or or 15-crown-5, tetramethylethylenediamine or lithium dibenzo-18-crown-6 for triethanolamine and potassium (see Chem, Rev., 1979.79. p. 415) ).

In another aspect of the method for preparing the homogeneous catalyst of the invention, the metal and Solvent additives can be used to accelerate the reaction of the alkoxide component components.

- By way of example, a nickel carbonyl activator, e.g. sodium sulfide, is added to the methanol solution. lithium, thioacetamide, mercury ion, e.g. borate ion derived from boric acid, porate esters, and thioamides, such as thiocarboxylic acid amides, thioazoles, thioamides, Ourea, mustard oil, thiocarbamic acid derivatives, thiuram disulfide, and low Rhodamic acid and the like can be added.

In preferred homogeneous catalyst formulations of the invention, the transition metal component is nickel tetracarbonate. It is a complex of rubonyl, the alkoxide component is a methoxide anion, and the alkoxide component is a methoxide anion. Preferred counterions are alkali metals (Na, K) or non-alkali metals, e.g. Tetramethylammonium, these preferred cations are methanol solvent The solubility of the catalyst components dissolved therein is increased. The metal in the catalyst formulation of the invention and the proportion of alkoxide components, depending on whether methanol is used as the sole solvent or varies depending on whether or not a cosolvent is used. Basically, methanol-containing solutions Medium system II! The amount of metal and alkoxide in the metal compound is about 0. 0.01 to 2 mol, and for alkoxides 0.01 to 2 mol. C11-20 mol Varies within a range.

When methanol alone is used as a solvent, the preferred molar ratio is 1/100. , while when tetrahydrofuran is used as a co-solvent, the preferred molar The ratio is 110.5.

The reaction rate of the present invention in batch methanol synthesis is about 300 psi/min. Achieved using homogeneous catalysts. The simplicity of this active catalyst is such that the product, i.e. meth Nor acts as a solvent and the alkoxide component is derived from the product, resulting in This simplifies the mechanism of the reaction system and makes it economically attractive. There is a particular thing. Methanol as a product consists of unreacted as well as chemical reactions in the liquid phase. It can be removed from the reaction region as a gas along with the CO and other gases produced by the reaction. Book The catalyst of the invention has extremely high methanol synthesis selectivity. High meta of around 94% Nol conversion is consistently achieved. The rate at which ω and Hl react depends on the presence of a cosolvent. This can be enhanced by carrying out the reaction in the presence of Particularly recommended auxiliary solution The medium is T, 2-methyl T) IP, p-dioxane, t-amyl alcohol, t-Butyl alcohol, triglyme, and PEG-200 and PEG-40 It is a polyethylene glycol known as 0. The above co-solvent is methanol and They are used in equimolar or nearly equimolar amounts. But if necessary, more Or you can choose a smaller amount.

CO and H2 to produce methanol catalyzed by the homogeneous catalyst of the present invention Since the reaction occurs in a liquid reaction phase, feed gas is supplied to the catalyst to form a liquid/gas phase system. Contact can be made in any reactor designed for operation. Similarly, this methano Polymer production can be carried out in reaction systems designed for batch, semi-continuous or continuous reactions. can be administered.

This production of methanol can be carried out using the catalyst of the invention and with good mixing of the gas/liquid phases. Preference is given to carrying out using a reactor characterized by: raw methanol The composition contains excess carbon monoxide and hydrogen or an inert carrier gas such as nitrogen gas. can be taken out by blowing into the reactor. methanol as a gas The catalyst, its activity, lifespan and handling can be The technical benefits of the manufacturing process can be obtained. Also, methanol is taken out as a liquid phase and dissolved in The decomposed catalyst can also be removed with the product stream from the reactor. The product is The catalyst is evaporated in the separation zone and recycled to the reactor.

The low operating temperatures required by the catalyst of the invention and its high temperature with extremely short contact times In combination with high catalytic activity, the feed gas in the methanol synthesis can be This makes it possible to obtain a high conversion rate. - oxidized carbon at 100°C and 150psi The equilibrium conversion rate of syngas containing 2 moles of hydrogen per mole of hydrogen is equal to It was calculated to be approximately 94% throughout. Furthermore, the characteristic that the catalyst system of the present invention is liquid is that , from the reactor for gas-liquid contact for fast reactions and exothermic reaction of CO and H7. This makes it possible to separate the generated heat from the removal. This separation can be achieved by e.g. an external cooler or by condensing the catalyst outside the reactor and recycling it into the reactor. This can be done by incorporating into the catalyst system a recyclable inert low-boiling compound. Applicable High thermodynamic equilibrium of the process and ability to separate kinetics and heat transfer o decouple), the reaction imposed on conventional catalyst technology is Eliminates reactor design limitations.

In one embodiment of the invention, the homogeneous catalyst contributes as the transition metal carbonyl The substance and the substance contributing as the alkoxide are mixed with methanol and a predetermined auxiliary solvent. Prepared on-site in a reactor by adding to a solution containing a medium, activator, etc. be done. Methanol production can proceed immediately after preparation of the catalyst. one more In the method, the homogeneous catalyst of the present invention is prepared separately in advance and added to the reactor at the required time. You can.

In one embodiment of methanol synthesis using the liquid phase catalyst of the present invention, the raw material synthesis gas is The reactor is charged to a reactor operating at 110° C. and 150 psi. At that time, the gas It rises through the catalyst solution, producing methanol while releasing heat, which is e.g. It is removed by circulating a refrigerant through the reactor through a coil. This cooling system does not completely separate cooling from the reaction boundary conditions, but heat transfer to the coil is rapid. or, the reaction proceeds essentially isothermally at a preferred temperature. I mean, This is because the liquid is vigorously stirred and disturbed by the gas flow. as a result , - a conversion rate of 90% of carbon oxide can be achieved. Therefore, tail gas (tail g as) has a very small volume and requires a cooler, separator and recirculation of unconverted gas. Recirculation compressors for use with conventional heterogeneous catalysts require similar components. It is very small compared to the In small amounts of gas, vaporous methanol over It may not be sufficient to transport all the heads. In such cases, the applicable It is necessary to extract liquid from the reaction. This liquid is combined with the condensate from the separator. This constitutes the crude methanol flowing out of the separation system. Drain the liquid from the reactor The first distillation column separates the volatile catalyst components and transfers them to the reactor. return. The second distillation column produces methanol product as distillate. This method is meta When used in the preparation of alcohol and when a co-solvent is used in the system, the co-solvent is selected to have a higher boiling point than methanol, so methanol and the auxiliary The co-solvent is separated from the solvent in the second distillation column and the co-solvent is returned to the reactor as a liquid. Ru.

Synthesis gas is almost completely converted to methanol in just one pass through the methanol synthesis reactor. With the discovery of the low-temperature liquid catalyst of the present invention, which can The manufacturing method became possible. This feature allows the use of atmospheric nitrogen in the synthesis gas. The volume of gas supplied to the reactor is the volume of gas required in a conventional synthesis reactor. It is possible to make it smaller than. Table 1 below shows the method of the present invention and conventional methane A comparison with the roll catalyst method is shown. Significant improvements were made in both reaction conditions and product yield. Be looked at.

Table 1 Contact with a homogeneous catalyst, compared to the conventional contact 0 Production of MeOH by mediated MeOH production Reactor temperature, °C 110 265 Reactor pressure, psia 15 (1750 equilibrium ω conversion, % 9461 Operating CO conversion rate, % 9016 Gas circulation capacity, molar / product mole 0.11 5.25 reactor feedstock, CO mole / product mole 1 ．． 11 6.25 over rad gas cooling capacity, Btu/product mole 4.100 71.00095%’Separator temperature for product recovery,’F 163 77* 5upp, E, Hydrocarbon processing Processing), March 1981, pl), 71-75 and 1 bid, 1984. July, pp, 34C-34J0 The following examples are from this publication. The present invention is not limited to these Examples in any way. . In the examples described below, the total pressure in the reactor was approximately 7 65 psig to about 50-150 pstg at the end of the reaction. turned into The final pressure is equal to the predetermined operating pressure of the continuous reactor.

Example 1 30 m of NaH (40 m) and a slight excess of t-amyl alcohol (52 m) Sodium t-amyl alkoxy prepared by reacting in THF of 1 (40 nM) was added to the reactor with 70 ml of 1 to make a total of 1 ml of THF. 00m1. The reactor was flushed with H3. IOm Nj (CD) 4 was added, and synthesis gas (2Ht:Ic0) was injected into the reactor at 300 psig. did. 10 (first, second and third charges (each) lhs when heated to 1°C The gas consumption rate was 3.8.7 psi/min for each of Si). .

164 methanol was produced, corresponding to a gas consumption rate of 86%.

Example 2 This example shows the effect of alkali metals on reaction rates. Preparation of alkoxides and Reactor charging was carried out using potassium hydride instead of sodium hydride. The procedure described in I was repeated. Thus, K)l(40r fM) and t-amyl alcohol (52am). -1-amyl alkoxide was obtained. The obtained solution was charged into a reactor and 70ml of THF was added. The reactor was sealed, purged with Hl, and treated with 10mM Ni ( CO)4 was added. 300 psi of synthesis gas (2H,: Ic0) was added to the reaction. and the reactor was heated to 100°C. The average gas consumption rate is 1 (300psi), 2 (300psi), 3 (300psi) and 4 (750 psi) at 32, 50, 22 and 7.5 psi/min respectively. there were. 0.35 mol of methanol was produced.

Example 3 This example shows the effect of increasing alkoxide concentration on the reaction rate and shows that the method Shows true contact between the group and nickel. -t-amylalkoxy The procedure of Example 2 was repeated by increasing the amount of 406) to 100-. average gas The consumption rates were 1 (300 psi) and 2.3.4 and 5 (7 psi each) respectively. 54.275 and 64 psj/min, respectively. 1 molar of methanol was produced, corresponding to a gas conversion of 94%. Generated meta Nol for at least 100 cycles for Ni and 10 cycles for base. 2, which proves the contact nature of the present invention.

Example 4 In addition to the reagents described in Example 2, it contains the ligand 2,2-bipyridine (5mM) The mixture was heated to 100°C and stirred in the reactor and methanol (212 dl +) was generated.

The rate of pressure drop is for each of charges 1.2 and 3 (300 psi each) 90.28 and 12 psi/min. The gas consumption rate of methanol alone is 82 %.

Example 5 The procedure of Example 2 was repeated, but the reactor was replaced with the usual 2H,:ICO mixture. Rini N.

Methanol was prepared by pressurizing with syngas containing . The gas consumption rate depends on the charge l and and 2 (700 psi each; Nt 400 ps! and 2Ht:IcO combined 46 and +5 psi/min for the grown gas (300 psi), respectively. The N , the gas simply passed through the reaction system without affecting the catalyst. 639 reward Methanol was produced, which was estimated at >98x the total gas consumption rate.

Example 6 The procedure of Example 2 was repeated but with 8 instead of the regular 2Ht:ICO mixture. Prepare 153 m of methanol using a gas mixture containing 4-90% CH4. Manufactured. This is estimated to be >98% of the total gas consumption rate, so the methane is It was shown that it had no effect on activity.

Example 7 The procedure of Example 2 was repeated. However, the initial gas mixture contained H and S.

The gas extinguishing 11 rate is charging 1 (300 psi; containing 2X HtVc) Oyohi 2 (300 psi; Contains 4% H, S) 33 and 5 psi/ It was a minute. 238-methanol was produced.

This is estimated to be >99% of the total gas consumption rate, thus making the catalyst highly susceptible to S poisoning. It was shown to have good tolerance.

Example 8 For the preparation of alkoxide components, when K is used instead of punishment, the conversion rate A slight improvement was seen in the results. Thus, 4M di-t-amyl alkoxide ( prepared from potassium (40mM) and t-amyl alcohol (52-), and 10 A solution containing 0 ml of T)[F and 5-Ni(Co)4 was added to the reactor. heated to 100°C in the presence of 300 ps i of synthesis gas (2Ht:ICO). It was hot. 260-methanol was produced. Charges 1, 2 and 3 (300 ps each j) Gas consumption rates were 26.52 and 25 psi/min for each.

Example 9 The following experiment was conducted to determine the effect of the transition metal carbonyl catalyst component on the methanol synthesis rate. The effect of concentration was confirmed. The procedure and configuration of Example 8 was repeated, but with nickel steel. The concentration of tracarbonyl was varied. For charges 1, 2 and 3 (300 psi each) Table 2 shows the gas consumption rates.

It increases with increasing concentration of Tsukeru carbonyl. In either case, the manufacturing method is true. be in touch with

Example 1O , the gas consumption rates were 47 and 30 psi/min, respectively. this thing suggests that the catalyst of the present invention provides high volumetric efficiency.

Example 11 are 8.40 and 52 for charges l, 2 and 3 (300 psi each) respectively. psi/min.

Example 12 12.64 and 30 psi/min for 1.2 and 3, respectively. Ga The consumption rate depends on the nature of the alcohol used to produce the alkoxide. There is.

Example 13 ) was used. Significant improvement in gas consumption rate was observed (gas consumption rate was 74.31 and 22 psi/min for 1.2 and 3, respectively).

303 m of MeOH was generated, and the consumption rate of synthesis gas is estimated to be 97%. It was done.

Example 14 Dilute 0.1M tetramethylammonium methquinde with 50% p-dioxane. Dissolve in 100 mI diluted methanol and add 5mM Nj(CD). A completely homogeneous solvent was obtained.

800 psia of synthesis gas (2Ht:l CO) was injected into the reactor, and 120 psia It was heated to 'C. The methanol synthesis rate was 3 psi/min. This is similar The results were almost comparable to those obtained using 0CHs under normal conditions.

Example 15 The procedure described in Example 8 was repeated. However, the auxiliary solution m is the auxiliary solution listed in Table 3 below. Changed to solvent. The results of the gas consumption rates obtained are shown in Table 3 below.

2-Methyltetrahydrofuran 22 + 7 41.2 - diethoxyethane 3 4 12 4p-dioxane 25 49 23 N-methylmorpholine 40 12 3t-amyl alcohol 2 I- Polyethylene glycol (PEG-400) 52 32 - PEG400/Me Tanol (1:l v/v) 92 --- The homogeneous catalyst of the present invention is a co-solvent When using THF, p-dioxane or polyethylene glycol as It showed the highest effectiveness when

Example 16 Polyethylene glycol (PEG-400) in 100ml i:200+#)K Dissolve OMe and add 10#) Ni(Co) to obtain a completely homogeneous red solution. Obtained. 800 psia of synthesis gas (2H2:ICO) was pressurized into the reactor, and 1 Heated to 20°C. Methanol synthesis starts below 50°C, and the gas consumption rate is and 52 and 32 psi/min for and 2, respectively.

Example I7 50 methanol solvent! %PEG-400 and 400 dOMet' diluted, 10mM 17) Ni(Co)a was added to obtain a dark red catalyst solution. initial reaction The pressure of synthesis gas (2H1:l CO), which was 820 psia in the vessel, was 40°C. The pressure decreased to 49 psia with the onset of the reaction below. The methanol synthesis rate is 92 psi/min, and the highest temperature reached during the reaction was 115°C, which was the intended temperature. The temperature was 120°C. 296 methanol was synthesized, which was used for methanol selection. This corresponded to a selectivity of >98.5%. The final solution is red and completely homogeneous within 5 minutes. An ω conversion of 94% was achieved.

Example 18 Under an argon atmosphere, add 100 ml of 4 pieces of -1-amyl alkoxide. and 5-N1(CO)a were mixed together to obtain a red solution. 2 days at room temperature After standing for a while, the red solution was charged into the reactor and aoops i synthesis gas (2 H! :I Co) was injected, and then heated to 100°C. The activity of the premixed catalyst The properties were the same as the fresh catalyst solution described in Example 8.

Example 19 The effect of methanol accumulation and base concentration on the gas consumption rate was investigated using 5-nickel Tetracarbonyl, p-dioxane as co-solvent and as alkoxide K[)4e was used at 110° C. and 750 ps i. Display results 4.

75 25 400 ° 224 The results in Table 4 show that for a given base concentration, as the concentration of methanol increases, Gas consumption rate decreased. However, increasing only the base concentration can increase the consumption rate. I can do it. This base/methanol ratio relationship is described in the examples below.

Example 20 5-nickel carbonyl, 100 ml methanol and potassium methoxy A solution containing de is heated to a synthesis gas pressure of 7501]S! (2Hz: 1 co) under 110 Heated at ℃. At high base concentrations (>400m), the gas reaches a given temperature. It was consumed even before it was reached. The following results of this experiment indicate that the methanol synthesis rate is shows that the degree depends on the KOMe/MeOH (base/solvent) ratio.

6Cl (1>60 800 >>72 Example 21 containing 600 rIN of KOMe, 100 ml of MeOH and )i(CO)-. The catalyst solution was heated to 110 °C under a syngas pressure of 750 psi (2Hy:I CO). and heated. As shown in the data below, the reaction rate is It increased with increasing degree.

20 >>100 At high Ni(CO)4 concentrations (e.g. 20%), the gas produces methanol. Consumed within 3 minutes with formation.

Example 22 The effect of reaction temperature on methanol synthesis rate was investigated. 100-KOMe and 5 750 ps i in 100 ml of p-dioxane containing N1(CO)* When syngas 2Ht:IcO is injected, the gas consumption rate is 70.77.90 and 15, 43, 63 and 180 psi/min at 100°C, respectively. Ta. An Arrhenius plot is used for this reaction. +: 23.3 Kca 11 mol was given. Methanol synthesis requires high catalyst concentrations. The system starts at temperatures as low as room temperature, but this system has been successfully developed in the range of 50 to 150 °C. It progresses quickly.

Example 23 The catalyst system of the present invention is superior to conventional methanol as evidenced by batch reaction rate data. tolerance to some traditional catalyst poisons that adversely affect catalysts for synthesis have. Using the catalyst system of the invention containing 400 mM KOMe as described in Example 20. The various toxic effects when used are as follows.

(1) 75 (lpsi) containing 8% (1) CQt (the rest is 2H, :I Co) A 20% speed reduction was observed when using .

(2) 26% (7) Nt, 7.4% (7) (:Q, and 2.5% (7) H tS Thick i;! Using 750 ps i synthesis gas containing 2 Ht:l Co) In this case, the speed was reduced by 50%.

Example 24 In one embodiment of the invention, 3.0 g of dry zeolite 13XC at 400°C for 4 hours (dry under vacuum) in 100 ml of 400 m KOMe upon loading into the reactor. Added together with methanol solution. This reactor was heated to 750 ps i at 110°C. A synthetic gas (2Ht:ICo) was injected under pressure. The speed in this case includes zeolite The rate was 10% higher compared to that seen when using no catalyst solution. zeola The use of transition metal carbonyl supports such as carbonate has the following advantages: can get.

(1) Methyl formate, which is usually present in small amounts as a by-product, apparently disappears. and (2) N1(CD)4 is immobilized on the zeolite. By gas-phase infrared measurement If so, the gas phase concentration of Ni(CO)4 can be reduced by using a zeolite carrier. It was shown that

Example 25 Twenty batch experiments were conducted to determine temperature, methanol concentration, base concentration, Put, P. . The effects of , and stirring speed on the reaction rate were investigated. Table 5 is used in each experiment. The following conditions are shown below. All experiments used an initial Ni(CO)4 concentration of 0.05M.

However, in Experiments 1 and 2, 0.01M was used as the initial concentration. Experiment 21 uses methylformate as a solvent along with methanol, while all other The experiments used pure methanol or a methanol/p-dioxane mixture as the solvent. used.

The liquid phase concentrations of methanol, base, and 'cFNi(CO)4 listed in Table 5 are (1 ) There is no change in volume due to mixing of p-dioxane, methanol and m0CR. (2) It is assumed that there is no change in the density of the liquid phase in the range of 25°C to reaction temperature. I calculated it. Therefore, the concentrations of methanol, KOCH, and Ni(CO)4 are: More precisely it is stated in mol/l at 25°C.

Only experiments 1 and 2 had N1(CD)<concentration 0. It was carried out at OIM. I mean, These experiments were performed at catalyst concentrations that gave reasonable rates of reaction. Ru. A reasonable rate of reaction is from an initial pressure of 750 psig to a final pressure of 100-15 psig. 0 Defined as a speed that requires 2 minutes to 2 hours to descend to Qsig. Ta. The reaction rates in Experiments 1 and 2 are relatively slow and decrease further at the lower temperatures of interest. It is expected that Therefore, in all subsequent experiments a high initial value of 0.1) 5M N1 (CD) 411 degrees was used. The concentration of N1(CO)< Gave.

Experiments 3 and 5 determined whether mass transfer limited the reaction rate in these experiments. This was carried out to determine the Experiments 4.7.9 and 11 are 116.70.9 respectively It was carried out at 8 and 87° C. to investigate the effect of temperature on the reaction rate. In experiment 6, Repeat experiment 4 under lower stirring speed to determine whether mass transfer limits the reaction rate. I looked into it. However, Run 6 was completed before the reaction temperature of Run 4 was reached.

Experiment 8 was the first experiment in which methanol was present from the beginning of the reaction. It was. This experiment was conducted at 90°C. This is because in a more concentrated methanol solution This is because the reaction rate was unknown. The reaction rate at 90℃ was slower than expected. won. Therefore, after conducting the reaction in the presence of methanol from the beginning, the total In all experiments, the reaction temperature was maintained at approximately 110°C.

Experiments 10112 and 13 to determine the effect of methanol on the reaction rate It was carried out in The initial concentrations of methanol used in these experiments were 25 and 25, respectively] 0 and 50% by volume. Experiments 14, I5 and 16 were also conducted using different catalytic base concentrations. The purpose of this study was to investigate the effect of methanol concentration on the reaction rate at different temperatures.

These experiments used initial concentrations of methanol of 25.75 and 100% by volume, respectively; and initial KOCH, performed at a concentration of 4.0M.

Experiment 17, in which Experiment 15 was repeated at a higher stirring speed, The purpose of this experiment was to investigate whether mass transfer affects the reaction rate. .

Experiments 18 and 19 correspond to repeating experiment 16 under high base concentration. To investigate the effect of base concentration on reaction rate in 00% methanol solvent It was carried out in Repeat experiment 19 using 10% by volume methylformate solvent. Experiment 2, which corresponds to It was carried out to find out whether

Furthermore, one experiment (Experiment 18) showed that N1(CD)4 and potassium methoxide were This was carried out for the purpose of investigating whether it is not consumed during the reaction and functions as a catalyst. child 381 experiments were conducted, and each time the reaction progressed and the pressure was lowered below 200 ps This was done by repeatedly pressurizing the reactor with synthesis gas.

Experiment Stirring speed Initial KOMe Initial p-dioki Initial XITMeOH concentration etc. Temperature reaction No.'' (RPM) Concentration (M) San concentration (7%) (vo1%) (M) Temperature (℃) lb1200 0.4 100 0 0 +2021 12 00 0.4 100 0 0 1103 800 0.4 100 0 0 1204 1200 1.0 100 0 0 1165 1200 0.4 100 0 0 1206 500 1.0 100 0 0 11 (1? 1 200 1.0 100 Q Q, 7θ8 1200 1, (175258,2 90912001, (11000098 1012001,0?5 25 6.2 11011 1200 1.0 10 0 0 0 8712 1200 1.0 90 10 2.5 11013 1200 +, 0 50 50 12.4 +09+4 1200 4.0 7 5 25 6.2 10715 1200 4.0 25 75 18.5 1 1016 1200 4.0 0 100 24.7 11017 1800 4.0 25 75 18.5 10918 1200 8.0 0 100 24.7 11019 1200 6.0 0 100 24.7 10920 c+200 6.0 0 90 22.2 110a: Total solvent used = total In the experiment, 100 m1゜b: [Ni(CO)4] = 0. OIM; all other [:N1(Co), ) = 0.05 M for all experiments.

Lovol% methylformate was used instead of cap-dioxane.

Example 26 The following example demonstrates the synergistic effect of bimetallic systems in methanol synthesis. l-N 100 ml of 1(Co) 5-component copper methoxide and 0.6M KOCHz of methanol. The reactor was pressurized with synthesis gas (2Ht:l Co) and The mixture was heated to 120°C. Methanol was produced at a rate of approximately 5 psi/min.

Example 27 5 compounds of N1(Co)4 and 0.4M KOMe in 30% methanol/70% trichloride. Added to a solution of ethylene glycol dimethyl ether (triglyme) in a mixture. Add H! to the reactor. Synthesis gas with a /CO ratio of 2:1 was injected. This reactor When heated to 120° C., it exhibited a syngas consumption rate of +15 psi/min.

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Claims (28)

[Claims] 1. For producing methanol from carbon monoxide and hydrogen at low temperature and low pressure. A homogeneous catalyst comprising a transition metal carbonyl complex and an alkoxide, the transition metal genus or group consisting of Cu, Ni, Pd, Mo, Co, Ru, Fe and mixtures thereof selected from methanol and dissolved in methanol solvent alone or mixed with a co-solvent. The above homogeneous catalyst. 2. Claimed in which the transition metal is selected from the group consisting of nickel, molybdenum and copper. Catalyst according to scope 1. 3. A catalyst according to claim 1, wherein the transition metal is nickel. 4. Tetrahydrofuran, p-dioxane, l-amyl alcohol, t-butyl using a co-solvent selected from the group consisting of alcohol and polyethylene glycol. The catalyst according to claim 1 for use. 5. The alkoxide component is derived from an aliphatic alcohol having 1 to 6 carbon atoms. The catalyst according to claim 1. 6. The transition metal carbonyl complex is a nickel tetracarbonyl complex, and the transition metal carbonyl complex is a nickel tetracarbonyl complex; The lucoxide component is methoxide, and the catalyst is auxiliary with THF such as methanol. A catalyst according to claim 1 dissolved in a solvent system. 7. The transition metal carbonyl complex is a nickel tetracarbonyl complex, and the transition metal carbonyl complex is a nickel tetracarbonyl complex; The rukoxide is methoxide, and the catalyst is a combination of methanol and p-dioxane. A catalyst according to claim 1 dissolved in a co-solvent system. 8. The transition metal carbonyl complex is a nickel tetracarbonyl complex, and the transition metal carbonyl complex is a nickel tetracarbonyl complex; Rukoxide is methoxide, and the catalyst is methanol and polyethylene glyco be dissolved in a co-solvent system with a derivative of polyethylene glycol or polyethylene glycol. The catalyst according to claim 1. 9. Methanol is removed from carbon monoxide and hydrogen at low temperature and pressure in a methanol solvent system. A catalyst for producing a transition metal carbonyl or a metal carbonyl bricasa or any cluster thereof and the methanol by reaction with metal or amine compounds to form alkoxides in the presence of a solvent system. The above-mentioned catalyst is characterized in that it is prepared by: 10. the transition metal carbonyl reagent is nickel tetracarbonyl, and the transition metal carbonyl reagent is nickel tetracarbonyl; With rukoxide-forming reagents or aliphatic alcoholates of alkali or alkaline earth metals A catalyst according to claim 9. 11. Claim 10, wherein the alkoxide-generating reagent is potassium methoxide. Catalysts as described. 12. The alkoxide generating reagent is tetramethylammonium methoxide. The catalyst according to claim 9. 13. The alkoxide is a mixture of potassium methoxide and copper methoxide. This supplies methoxide ions and nickel tetracarbonyl/copper carbon. 10. The catalyst according to claim 9, which forms a bonyl complex. 14. Claim 9, wherein said methanol solvent system comprises methanol and a co-solvent. catalyst. 15. The catalyst according to claim 9, wherein the carrier for the transferred metal carbonyl reagent is added. . 16. 16. The catalyst according to claim 15, wherein the carrier is a zeolite. 17. Synthesis gas is dissolved in methanol or a mixture of methanol and a cosolvent. A method for producing methanol from the synthesis gas by contacting it with a homogeneous catalyst, the method comprising: The catalyst includes a transition metal carbonyl complex and an alkoxide, and the transition metal is Cu, selected from the group consisting of M, Pd, Mo, Co, Ru, Fe and mixtures thereof. The above method for producing methanol, characterized by: 18. The selected metal is nickel and the alkoxide is an aliphatic alcoholate. and the methanol young THF, methyl THF, p-dioxane, t-amyl A supplement selected from the group consisting of alcohol, polyethylene glycol and derivatives thereof. 18. The method of claim 17, used in conjunction with a co-solvent. 19. 19. The method of claim 18, wherein said alkoxide is methoxide. 20. Low temperature in the range of 100-150℃ and low pressure in the range of 100-150psi 18. The method of claim 17 comprising the use of conditions. 21. The transition metal carbonyl complex is a nickel tetracarbonyl complex, and the transition metal carbonyl complex is a nickel tetracarbonyl complex; The alkoxide is a methoxide derived from potassium methoxide, and the solvent system is Tanol, ThF, p-dioxane, polyethylene glycol and its derivatives 18. The method of claim 17, further comprising a co-solvent selected from the group consisting of: 22. Claim 17, wherein a transition metal carbonyl activator is added to the reaction solution. Method described. 23. 23. The method of claim 22, wherein said activating agent is sodium sulfide. 24. 23. The method of claim 22, wherein said activator is boric acid. 25. A substance that inactivates the cation bonded to the alkoxide is added to the reaction solution. 18. The method according to claim 17, wherein the method is added to 26. 26. The method of claim 25, wherein said deactivating agent is a crown ether. 27. 18. The method of claim 17, wherein the synthesis gas comprises an inert gas. 28. A homogeneous catalyst containing a complex of Ni(CO)4 and OCH3- was placed in a closed reactor. CO and H2 were introduced at an initial pressure of about 700 psi and a final pressure of about 115 psi. Then p-dioxane is introduced as a co-solvent for CH3OH to convert the catalyst into liquid form. from the gaseous reagents CO and H2, including the step of converting the resulting methanol into A method of producing methanol.