Homogeneous catalyst for methanol synthesis, method thereof and method for producing methanol

 

(57) Abstract:

Homogeneous catalyst for synthesis of methanol from carbon monoxide and hydrogen, containing the following components, mmol: carbonyl complex of a transition metal selected from the group comprising copper, Nickel, cobalt, molybdenum, ruthenium or mixtures thereof 1-20; anion f-ly AM-OR, where AM-PA, K, NMe+4, OR-derived (C1-C5) aliphatic alcohol 40-800, the carbonyl complex of the transition metal/AM-OR, the ratio of 2:800, solvent-methanol not more than 2500, the co-solvent is not more than 1500. A method of producing a catalyst by reacting carbonyl transition metal, alkali metal or amine derivatives in the presence of the system methanol-co-solvent selected from the group comprising tetrahydrofuran, para-dioxane, dreamily alcohol, polyethylene glycol dimethyl ether. A method of producing methanol from synthesis gas in the presence of the above catalyst at 100-150C and the pressure 7,03-10,55 kg/cm2. 4 C. and 21 C.p. f-crystals, 5 PL.

The invention relates to a new homogeneous catalysts for methanol synthesis from CO and H2, method thereof and method of producing methanol using a homogeneous catalyst.

When using the and overheating in the reactor, impede the effective development process. Moreover, the catalysts of the traditional type, for example, catalysts in the form of tablets, usually show the extent of the gas conversion of about 16-30% per pass and require recirculation of the source gas to provide the operation of a technological system with economical efficiency. Although partial oxidation of natural gas leads to the output of an ideal gas as feedstock for methanol synthesis, the specified partial oxidation cannot be used for a downloadable strip in traditional catalytic systems, as such systems require that the source of the raw material gas contained very low concentrations of inert gases, especially nitrogen. Inert gases such as nitrogen, contained in the flow of recycle gas to the effectiveness of the process should be kept at a low level. To obtain a raw gas with a low content of inert gases, as a rule, it is necessary to conduct a partial oxidation using oxygen, and this approach makes the method of obtaining the raw material gas is economically unacceptable.

In addition, as a rule, traditional methods require synthesis at high temperatures (250ois the being (60%).

The literature also describes the use of homogeneous catalytic systems for the synthesis of methanol or other lower aliphatic alcohols from carbon monoxide and hydrogen in a liquid phase environment.

Thus, the known homogeneous catalytic system comprising tirutani dodecanoyl, the promoter of the rare earth metals and oxide tri-n - propylphosphine as solvent. Synthesis with the use of this system is carried out at a temperature of 100-400oAnd pressure of 500-15000 psi. [1]

Also known homogeneous catalytic system comprising an alcoholate of an alkali metal, a copper catalyst, methanol and co-solvent in the amount of at least 50% (vol.). The process of methanol synthesis is carried out at temperatures in the range 90-130oAnd pressure 75-900 psi. [2]

Most closely related to the number of matching signs and the achieved result for the synthesis of lower aliphatic alcohols is homogeneous catalytic system comprising a transition metal carbonyl, dicarbonyl of dimalanta, formate, bicarbonate, or carbonate of alkali or alkaline-earth metal, methanol and co-solvent. The synthesis is carried out at 200 - 300oC and a pressure of 100-400 atmospheres.

The specified catalyst receive widenesses or alkaline-earth metal. [3]

Known homogeneous catalytic compositions of the present invention eliminates some of the shortcomings inherent in the conventional solid-phase catalysts for methanol synthesis.

So, due to the fact that the homogeneous catalyst used in the solution, the heat dissipation as a result of interaction can be realized regardless of the kinetics of the process. Thus, unlike traditional methods of optimal mode can be changed as chemical and thermal point of view in the technological system separately, optimizing the heat and adjusting the speed of the process.

When using the catalysts of the present invention, the methanol synthesis can be performed at low temperatures and pressures with a high degree of conversion in the equilibrium state.

Moreover, the proposed catalytic system unlike traditional enables you to use the method of partial oxidation of natural gas to produce raw synthesis gas, as a high degree of conversion eliminates the use of recycle gas stream and thus can be disposed of air instead of oxygen, which leads to a reduction in large difficult is the procedure, to carry out the conversion process in one pass, is that atmospheric nitrogen input into the system through a stage of partial oxidation air exits the reactor at a pressure of reaction, while it may increase in volume with the formation of energy, for example, to compress the air.

The present invention provides a homogeneous catalyst, which makes it possible to produce methanol from synthesis gas as a raw material containing inert gases at low temperatures and pressures, as well as high performance gas conversion. The specified catalyst significantly improves the reaction conditions and the efficiency of the process compared to traditional catalysts used in methanol synthesis.

The homogeneous catalyst of the present invention does not cause any problems, it shows high activity as compared with conventional catalysts used in methanol synthesis, makes possible the use of low temperatures and pressures in the reactor, allows you to use a raw material gas containing an inert gas in addition to CO and H2and leads to a high rate of the gas conversion.

We offer the AI contains a complex of a transition metal carbonyl, selected from the group comprising copper, Nickel, cobalt, molybdenum, ruthenium and mixtures thereof, and ALCOHOLATES componentmolar General formula: AM-OR, where AM Na+TO+N(Me4)+, OR-balance WITH1-C5-aliphatic alcohol solvent is methanol and the organic co-solvent in the following ratio of components, mmol:

The complex of the transition metal carbonyl 1-20

Alcoholate component 40-800

The solvent is methanol not more than 2500

The co-solvent is not more than 1500

The ratio (in moles) of the complex of the transition metal carbonyl and ALCOHOLATES component is 1:2-800.

The difference of the catalyst from the closest on the qualitative and quantitative composition of the catalyst [3] is that it contains as a carbonyl complex of a transition metal complex comprising a transition metal carbonyl selected from the group: copper, Nickel, cobalt, molybdenum, ruthenium and mixtures thereof and ALCOHOLATES component of the alcoholate of the General formula AMOR, where AM-TO+, Na+N(Me4)+, OR-the remainder of the C1-C5aliphatic alcohol with the above ratios.

Preferred catalysts are Nickel, molybdenum and copper, preferably Nickel; as a co-solvent is a co - solvent, selected from the group of tetrahydrofuran, p-dioxane, tert.-amyl or tert.-butyl alcohol, polyethylene glycol.

The most preferred catalysts containing as a carbonyl complex of the transition metal tetracarbonyl Nickel, as alcoholate - methylate, dissolved in the cosolvent system consisting of methanol and tetrahydrofuran or methanol, and p-dioxane or methanol and glycol or dimethyl ether or dimethyl ether, triethylene or tetraethyleneglycol.

According to the present invention it is also proposed a method of obtaining the above-mentioned homogeneous catalyst, which is that the carbonyl transition metal, or its precursor, selected from the group of metal: copper, Nickel, cobalt, molybdenum, ruthenium or mixtures thereof, is subjected to the interaction with the reagent, which forms an alcoholate of an alkali metal or amine derivatives in the presence of a system of methanol and the organic co-solvent selected from the group comprising tetrahydrofuran, p-dioxane, tert.-amyl or tert.-butyl alcohol, polyethylene glycol.

Profile the use of the above carbonyl complex of the transition metal or its precursor reagent, forming in the conditions of the reaction of the alcoholate of an alkali metal or amine derivatives, and solvents.

It is preferable to use as carbonyl transition metal tetracarbonyl Nickel, as a reagent, forming the alcoholate ion1-C5the alcoholate of an alkali metal, preferably potassium methylate or Tetramethylammonium. Preferably use as ALCOHOLATES reagent mixture of potassium methylate and methylate copper, carbonyl transition metal tetracarbonyl Nickel, which are in the process of interaction form methylate-ion and complex tetracarbonyl Nickel/carbonyl copper. It is also possible introduction in the process of transition metal carbonyl on the media, which mostly use zeolite.

The objective of the invention is also developing a method of producing methanol from carbon monoxide and hydrogen using a new homogeneous catalyst.

The closest to the number of matching characteristics to the achieved result is a method of producing methanol in the mixture with ethanol interaction of carbon monoxide and hydrogen in the presence of a catalytic system comprising the carbonyl is of propylphosphine. The process is conducted at 100-350oWith, mainly 195-240oAnd pressure 35-1400 ATM.

The main disadvantage of this method is the overwhelming amount of ethanol.

A method of producing methanol according to this invention consists in contacting the synthesis gas with a homogeneous catalyst comprising a complex of a transition metal carbonyl selected from the group comprising copper, Nickel, cobalt, molybdenum, ruthenium or mixtures thereof, and ALCOHOLATES component of the alcoholate of the General formula AMOR, where AM+, Na+NO(Me)4, OR-- balance WITH1-C5aliphatic alcohol, dissolved in methanol or in a mixture of methanol and co-solvent, in a ratio of components, mmol: the complex of the transition metal carbonyl 1-20; ALCOHOLATES component 40-800; solvent methanol to 2500; a co-solvent to 1500 when the ratio of the transition metal complex:alcoholate component AMOR/l:2-800.

Mainly as a transition metal to use Nickel as the alcoholate WITH1-C5-alcoholate, preferably To methylate or Na, and the methanol to be used in conjunction with the co-solvent, selected from the group of tetrahydrofuran, methylpyridine, p-dioxane, tert-amyl spyri complex carbonyl transition metal tetracarbonyl Nickel and methylate, obtained from methylate, and as solvents methanol and co-solvent selected from the group comprising tetrahydrofuran, p-dioxane, glycol dimethyl ether, triethylene or tetraethyleneglycol.

The optimal process conditions are set to low temperature in the range from 100 to 150oWith low pressure 7,03 - 10,55 ATM.

In the reaction mass, it is desirable to introduce inactivator carbonyl transition metal, in particular to enter inactivator cation associated with alcoholate ion. Mainly to introduce polyethylene, which reacts similarly crown-ethers.

Used synthesis gas may be diluted with an inert gas. A method of producing methanol is desirable to carry out the introduction of the homogeneous catalyst consisting of tetracarbonyl Nickel and potassium methylate in a sealed reactor, followed by the introduction of CO and H2when the initial pressure 52,73 bar and a final pressure of about 8,08 ATM transfer catalyst in the liquid phase with the separation of methanol from the resulting solution.

Homogeneous catalyst of the present invention consists of two components, dissolved in methanol or mixtures of methanol with chorustorete is the alcoholate. The transition metal is chosen from the group consisting of copper, Nickel, cobalt, ruthenium, molybdenum, or mixtures thereof. The preferred transition metal is used Nickel.

The proposed two-component catalyst presents in a solution of methanol formed from the methanol product in the reactor. You can also use any co-solvent, preferably an organic oxygen-containing the co-solvent, which has the ability to mix with methanol. To the preferred co-solvents include tetrahydrofuran, 2-methyltetrahydrofuran, para-dioxane, tertiary amyl alcohol, tert.-butanol, polyhydric alcohols, derivatives of glycols, such as polyethylene glycol and trigem.

Because the proposed catalyst has high activity, catalytic method of producing methanol from CO and H2can be done in moderate mode. The specified catalyst operates effectively at temperatures in the range from 20 to 150oC, and the temperature interval from 100 to 150oWith preferred. Similarly, pressure, mainly generated in the reactor may be lower 3,515 kg/cm2and above 21,09 kg/cm2.

As the materials the C-gas, produced by partial oxidation of natural gas in the presence of air. Specified raw material gas may be diluted with inert gases, such as nitrogen and methane. In the feed gas may be the presence of minor amounts of hydrogen sulfide, carbon dioxide and water, but it is preferable to use almost waterless, not containing CO2synthesis gas.

The proposed homogeneous catalyst is a product of the interaction of the two reagents used for this catalyst, in particular the compound of the transition metal alcoholate. The transition metal compound is a substance that can form the corresponding carbonyl transition metal in methanol solution. The compound of the transition metal may be a metal carbonyl or carbonyl precursor. The term "carbonyl precursor", as used herein, means a material that, when dissolved in methanol forms a carbonyl transition metal in situ. Carbonyl transition metal or the precursor of the transition metal carbonyl can be used to obtain the proposed catalyst in its single-core or cluster forms such as tetracarbonyl Nickel Ni(CO)4or any predecessor of carbonyl Nickel having the ability to form carbonyl nikeeta in methanol solution, can be used in the process of obtaining this homogeneous catalyst. You can also use a bimetallic system, which used a mixture of two carbonyl compounds of transition metals or their precursors, such as carbonyl Nickel and molybdenum carbonyl. In another case, the use of bimetallic systems carbonyl transition metal or its predecessor, such as tetracarbonyl Nickel, used in conjunction with the reagent, giving an alcoholate such as sodium methylate, and, in addition, you can also use the alcoholate of a transition metal, such as methylate copper.

Carbonyl transition metal or its product, the precursor can also enter in a solution of methanol on the media with the formation on its surface, for example, carbonyl Nickel. In this case, the homogeneous catalyst on the carrier type zeolite may act either as homogeneous or heterogeneous catalyst.

The second reagent used in the process of obtaining the proposed homogeneous catalyst is a material that gives alkoxides comp is / establishment, which constitutes or leads to the formation of the alcoholate in the presence of the system methanol/solvent, where CNS group formed from aliphatic alcohols with 1 to 5 carbon atoms.

The nature of the R group OR has no critical values. In the presence of methanol in the reactor predominant element affecting the methanol synthesis is the anion methylate ome-. Thus, initially used the alcoholate is reacted according to the following equation: RO-+ Meon - ROH + MeO+.

When alcoholate component is introduced into the reactor in the process of obtaining a homogeneous catalyst, you can also enter a reagent that inactivates the cation or ion-alcoholate during the physico-chemical interaction to increase the concentration of the alcoholate ion in solution. Suitable complexing and/or coordinating agents or ligands for these purposes include crown ethers, cryptand and polydentate cations of alkali and alkaline-earth metals. For your preferred complexing agents and/or ligands of the coordination compounds include 2,2'-dipyridyl, dimethyl ether of diethylene glycol or 15-crown-5 with sodium, tetramethylaniline or triethanolamine with lithium and dibenzo-18-crown-6 with potassium (see Chem. Rev. vol.79, page 415, 1979).

In the preferred composition of gomola Nickel, and as alcoholate use methylate-anion, MeO-and associated cation is either alkaline metal (Na, K) or Tetramethylammonium; these cations increase the solubility of the catalyst components dissolved in methanol solutions. The ratio of metal and ALCOHOLATES components in the catalyst varies depending on whether you are using a methanol in pure form as a solvent or in a mixture with another solvent. If methanol in pure form is used as a solvent, the preferred molar ratio is 1:100, while when using tetrahydrofuran as a co-solvent, the preferred molar ratio is 1:0.5 in.

When using homogeneous catalysts of the invention is achieved, the feed rate of raw material for the synthesis of methanol over 21,09 kg/cm2/min. Simplicity specified under consideration of the catalyst lies in the fact that the product (methanol) simultaneously serves as the solvent and of the specified product can be obtained alcoholate component, thereby making the catalytic system is simple from the point of view of its mechanism of action and cost-e gas simultaneously in the reaction in the liquid phase. The specified catalyst has an extremely high selectivity for methanol synthesis. When this reaches a stable value conversion in methanol up to 94% When carrying out the reaction in the presence of co-solvent can increase the speed of interaction WITH and H2. Particularly preferred co-solvents include tetrahydrofuran, 2-methyltetrahydrofuran, para-dioxane, tertiary amyl alcohol, tert. -butanol, trislim and glycols, known as PEG-200 and PEG-400. The above co-solvents preferably used in equimolar or nearly equimolar amounts relative to methanol. If desired, however, you can also find larger or smaller than their dosage.

Due to the fact that the reaction between CO and H2for the production of methanol, catalyzed offer a homogeneous catalyst is in the liquid phase, the source gas can be fed to the catalyst for their direct interaction in any reactor that is designed for operation in the system liquid/gas. The methanol synthesis can be performed in a reactor system, designed for continuous, semi-continuous or batch process.

Preferably, Contessa by mixing the gas and liquid phases. Methanol is removed from the reactor by passing through the reactor WITH excess and H2or inert carrier gas, for example nitrogen. When removing the methanol in the form of gas reach the relative advantages of the proposed technology associated with the specified catalyst, its activity, lifetime and processing. Alternatively, methanol can be distinguished in the liquid phase, while the dissolved catalyst is carried by the flow of product from the reactor. Products are then subjected to instantaneous evaporation in the zone for the separation and the separated catalyst is introduced into the reactor to recirculatory.

The combination of low operating temperature, which is required when using the proposed catalyst, and its high catalytic activity at very short in contact allows you to reach a very high degree of conversion of the raw material gas for methanol synthesis. The equilibrium conversion of synthesis gas containing 2 mol of hydrogen per mol of carbon monoxide at 100oAnd 10,55 kg/cm2as consistently show analyses, approximately 94% moreover, the liquid nature of the proposed catalytic system allows you to stop contacting the gas in the solution for reriani contact can be realized, for example, by circulating gas through an external cooler, or by introducing an inert low-boiling reactant in the catalytic system, which can be cooled from the outside and entered for recirculation to the reactor. The combination of high thermodynamic equilibrium process and the ability to separation kinetics and heat transfer leads to the elimination of restrictions to reactor design currently available technologies for the production of catalysts.

According to the present invention a homogeneous catalyst may be obtained in situ in the reactor by introducing component-based transition metal carbonyl and ALCOHOLATES component in a solution of methanol, and the required co-solvents, activators, etc. the methanol Synthesis may begin immediately after the formation of the catalyst. Alternatively, the homogeneous catalyst can be obtained in advance outside of the reactor with subsequent loading into the reactor, if necessary.

In another embodiment, synthesis of methanol using a catalyst, in the liquid phase, the raw synthesis gas is introduced into the reactor, operating at a temperature of 110oAnd pressure 10,55 kg/cm2. The gas passes through the solution catalystic reactor. Although this cooling system is not fully removes heat of reaction, heat transfer to the coil occurs quickly, and the reaction proceeds essentially isothermal under favorable temperature regime due to intensive mixing and turbulence of the specified liquid catalyst, due to the gas flow. Volume of exhaust gas is negligible, and the cooler, separator and the compressor for recycling of unconverted gas have very small dimensions in comparison with requirements similar to those used in conventional heterogeneous catalysts. A small amount of gas may be insufficient to transfer the whole of the upper ring-methanol in the form of steam. In this case, it is necessary to separate the liquid from the reaction product. Specified fluid is then mixed with the condensate from the separator separating the crude methanol, which flows down from the specified separator systems. When removing the fluid from the reactor in the first distillation column separates the volatile catalyst components and their return to the reactor. In the second distillation column is formed methanol in the distillate. When using this method for the synthesis of methanol, eraut with a boiling point below the boiling point of methanol, resulting methanol and co-solvent are separated from each other in the second distillation column, and the co-solvent return again to the reactor in the form of any liquid forms.

A method of producing methanol according to the present invention using low-temperature liquid catalyst leads to almost complete conversion of synthesis gas to methanol in a single pass through the reactor in the process. This allows the presence of atmospheric nitrogen in the synthesis gas and the volume supplied to the reactor gas is less than the required volume of gas in modern reactors for methanol synthesis. The table below provides a comparative analysis of the proposed technology and traditional catalytic process for the synthesis of methanol. Significant improvement of the reaction conditions, and increasing product yield (see table.1).

The following additional examples illustrate the present invention but it is not limited to these examples. In these examples, below, the total pressure in the reactor ranges from about 53,85 kg/cm2at the beginning of each passage to approximately 3,515-10,55 kg/cm2at the end, and this pressure is at the stage several 1.

Tert-adalat sodium (40 mmol), obtained by the reaction of NaH (40 mmol) with a slight excess of tert-amyl alcohol (32 mmol) 269 mmol of tetrahydrofuran is introduced into the reactor together with the 860 mmol of tetrahydrofuran with getting 1229 mmol THF in total. Then the reactor was rinsed H2. Added 10 mmol of Ni(CO)4and injected into the reactor synthesis gas at a pressure 21,09 kg/cm2(H2:/2:1). After heating the reaction mixture to 100oWith the gas flow rate is 0,21;, 56; 0.49 kg/cm2/min, respectively during the first, second, and third boot (with pressure 21,09 kg/cm2each), respectively. Get 164 mmole methanol, which corresponds to 86% of the gas flow.

Example 2.

This example shows the influence of alkali metal on the feed rate. Getting alcoholate and loading of raw materials in the reactor is carried out according to the method of example 1, except that instead of sodium hydride take potassium hydride. Thus, 40 mmol of tert-Aminata potassium receive when interacting KN (40 mmol) 52 mmol of tert-amyl alcohol 269 mmol of tetrahydrofuran. The resulting solution was poured into the reactor and adding another 860 mmol THF. The reactor is sealed and let H2and then the R and the reactor heated to 100oC. the Average gas flow rate is 2.25; 3,51; 1,54; 0,56 kg/cm2/min at downloads 1 (21,09 kg/cm2), 2 (21,09 kg/cm2), 3 (21,09 kg/cm2), 4 (52,73 kg/cm2) respectively. Get to 0.35 moles of methanol.

Example 3.

This example illustrates the positive influence of increasing concentrations of alcoholate to the consumption of raw materials, as well as the fact that the process is truly catalytic in the presence of a base and Nickel. The concentration of tert-Aminata potassium increased to 110 mmol instead of the previously used 40 mmol and repeat the procedure described in example 2. The average gas consumption is 3,797; 2,18; 4,50 kg/cm2/min at downloads 1 (21,09 kg/cm2), 2, 3, 4 and 5 (each pressure 52,73 kg/cm2). Get 1 mol of methanol, which corresponds to 94% of the gas conversion. Methanol obtained corresponds to at least 100 cycles when using Ni and 10 cycles when using Foundation, which confirms the catalytic nature of the invention.

Example 4.

The methanol in the amount of 212 mmol get when heated to 100oC and stirring in the reactor mixture containing the ligand 2,2'-dipyridyl (5 mmol), in addition to the reagents described in example 2. The flow rate of the materials is 2) respectively. The output of methanol in pure form is 82% of the gas flow.

Example 5.

Follow the procedure of example 2 except that the reactor pump synthesis gas containing Ni (instead of the traditional mixture of N2:/2:1). The result is methanol. The gas flow is 3,234 and 1,055 kg/cm2/min, respectively while downloading 1 and 2 (52,73 kg/cm2each containing N2compressed at a pressure of 28,12 kg/cm2and synthesis gas (H2:/2:1), respectively. N2passes through the system without influencing catalyst. Receive 639 mmol of methanol, which is more than 98% of its output from the total gas consumption.

Example 6.

Follow the procedure of example 2 except that the gas mixture contains from 84 to 90% of CH4instead of the usual mixture of N2and WITH (2:1). Get 153 mmole methanol, representing 98% of its output from the total amount of gas consumed in the production process, suggesting that methane does not adversely affect the catalyst activity.

Example 7.

Follow the procedure of example 2 except that the source gas mixture contains H2S. the Flow rate of the gas containing 2% H2S) and 2 (compressed gas mixture at a pressure 21,09 kg/cm24% H2S), respectively. Get 238 mmol of methanol, which is more than 99% of the output from the total gas flow, suggesting that the proposed catalyst has a high resistance relative to toxic hydrogen sulfide.

Example 8.

A slight increase in the depth conversion, when to get alcoholate as a component of the proposed catalyst instead of KN are used To. so, a solution containing 40 mmol of tertiary Aminata potassium (from potassium (40 mmol) and tert-amyl alcohol (52 mmole), 1229 mmol THF, and 5 mmol of Ni(CO)4, heated to 100oWith the reactor entered into it with compressed synthesis gas (H2:/2:1) at a pressure of 21,09 kg/cm2. Get 260 mmol of methanol. Consumption is 1,828, of $ 3,656 and 1,758 kg/cm2/min at downloads 1, 2 and 3, respectively (each at a pressure of 21,09 kg/cm2).

Example 9.

To study the effect of the concentration of carbonyl transition metal component of the catalyst on the rate of synthesis of methanol is performed following experimenty. Use the procedure described in example 8, except that varies MESI to download 1, 2 and 3, respectively (each compressed at a pressure of 21,09 kg/cm2).

At a given concentration of the base (40 mmol in this case), the consumption rate increases with increasing concentration of carbonyl Nickel, but the relationship is not linear. In each case, the process is catalytic in nature.

Example 10.

This example shows that the catalytic activity in methanol synthesis does not depend on the volume of the solvent. Tert-adalat sodium (40 mmol) are loaded into a Parr reactor with a capacity of 300 ml with 246 mmol THF. After blowing hydrogen into the reactor introducing synthesis gas (H2:/2:1), compressed at a pressure of 21,09 kg/cm2. The gas flow is 2,531 kg/cm2/minutes To download 2 and 3 (each, compressed at a pressure of 21,09 kg/cm2), the flow rate of the gas mixture is 3,305 and 2,109 kg/cm2/min, respectively, indicating a high volume productivity with the use of the catalyst.

Example 11.

On the rate of methanol synthesis is affected by the ratio base:Nickel. For example, when the repetition of one of the experiments of example 9 using the ratio of grounds to Nickel 100 mmol/1 mmol (100:1) consumption is 0,562, 2,8 the example 12.

Repeat the procedure described in example 8, except that instead of tert-Aminata use potassium 40 mmol of potassium tert-butylate (obtained from K and tert-butanol). The gas flow is services, 0.844, 4,500 and 2,109 kg/cm2when the loads 1, 2 and 3, respectively. Consumption depends on the nature of the alcohol from which the alcoholate.

Example 13.

Repeat the experiment described in example 8 using 40 mmol of potassium methylate (Coma) (specified alcoholate derived from the Meon primary alcohol unlike tert-Aminata and potassium of potassium tert-butylate, which are derived from tertiary alcohols), with significant performance improvement (5,18, 2,17 and 1,547 when downloads 1, 2 and 3, respectively). Get 303 mmole Meon, which is 97% yield from consumed synthesis gas.

Example 14.

to 0.1 mol of methylate Tetramethylammonium dissolved in 2500 mmol, diluted 50% para-dioxane and added 3 mmol of Ni(CO)4to obtain a completely homogeneous mixture. In the reactor, creating pressure 56,25 kg/cm2with the introduction of synthesis gas (H2:/2: 1) heating the reactor to 120oC. Performance of the methanol synthesis is 0,211 kg/cm2/min, which is comparable tx2">

Repeat the procedure described in example 8, except that instead of tetrahydrofuran using a co-solvent, are given in table 3. Consumption data are given in table 3.

We offer a homogeneous catalyst operates more efficiently when using THF, para-dioxane or glycol as co-solvent.

Example 16 (polyethylene glycol).

Being an excellent co-solvents, glycols differ in that they react similarly crown-ethers in the process of encapsulation of alkali metals.

200 mmol dissolved in a Coma 282 mmol of polyethylene glycol (PEG), and then add 10 mmol Ni(CO)4obtaining a completely homogeneous solution is red. In the reactor lower pressure with the introduction of synthesis gas (H2:/2:1) at a pressure of 56,25 kg/cm2and heated to a temperature of 120oC. the methanol Synthesis begins at a temperature below the 50oC, and the gas flow rate is of $ 3,656 and 2.25 kg/cm2rpm at loads 1 and 2, respectively.

Example 17.

In another example, throw 50% PEG-400, and then add a Coma and 10 mmol Ni(CO)4with the formation of a solution of the catalyst tecture reduced to 3,445 kg/cm2with the beginning of the synthesis of methanol at a temperature below 40oC. the Rate of synthesis of methanol is 6,469 kg/cm2/min, and the highest temperature in the process of interaction is 115oWith, and the most preferred 120oC. Receive 296 mmol of methanol, while the selectivity of methanol is more than 98.5% of the Final solution is red and full homogeneity, thus attain 94% depth conversion WITH at least 5 minutes.

Example 18.

40 mmol of tert-Aminata sodium, 1229 ml THF and 5 mmol of Ni(CO)4stirred in the presence of argon to obtain a red solution. After 2 days, while keeping the solution at room temperature it is loaded into the reactor and heated to a temperature of 100oAfter creating pressure in the reactor 21,09 kg/cm2with the introduction of synthesis gas (H2:/2:1). Activity pre-mixed catalyst similar to that of the fresh catalyst solution described in example 8.

Example 19.

The effect of increasing concentrations of methanol and base on the performance of the process was studied at a temperature of 110oAnd pressure 52,73 kg/cm2when using 5 mmol of tetrabromomethane in table 4.

From table 4 it is seen that the flow rate is reduced by increasing the concentration of methanol at a given concentration of the base. However, in the case of a simple increasing base concentration and possibly increase the performance of the process. The relationship between the ratio of grounds to Meon described in the following example.

Example 20.

A solution containing 5 mmol of carbonyl Nickel, 2500 mmol of methanol and potassium methylate is heated at a temperature of 110oC at a pressure of synthesis gas (H2:/2: 1) 52,73 kg/cm2. With increasing base concentration (>400 mmol) gas consumed even before reaching the desired temperature. Below the results of this experiment indicate that the rate of synthesis of methanol depends on the ratio of Coma to the Meon (base to the solvent).

Coma (mmol) gas Consumption (kg/cm2/min)

400 0,773

600 >4,219

800 >>5,062

Example 21.

The catalyst solutions containing 600 mmol Coma, 2500 mmol Meon and Ni(CO)4, heated to 110oC at a pressure of synthesis gas 52,73 kg/cm2(H2:/2: 1). As can be seen from the following data, consumption increases with increase in the concentration of carbonyl Nickel.

Ni(CO)44(for example, 20 mmol), gas completely conversores after 3 minutes with the formation of methanol.

Example 22.

The influence of reaction temperature on the rate of methanol synthesis. When 100 ml (1174 mmol) of para-dioxane, containing 100 mmol Coma and 5 mmol of Ni(CO)4, compress to 52,73 kg/cm2with the introduction of synthesis gas (H2:/2: 1), the gas flow is 1,055, 3,023, 4,43 and 12,66 kg/cm2/min, respectively, at temperatures of 70, 77, 90 and 100oC. To this reaction get the curve Arrhenius equation of Epact= 23,3 kcal/mol. The methanol synthesis begins at a temperature below room temperature when using higher concentrations of catalyst, however, the system is effective in the range from 50 to 150oC.

Example 23.

The proposed catalytic system can withstand the action of a number of conventional catalytic poisons, which have a negative impact on the well-known catalysts used in methanol synthesis, which is confirmed by the efficiency of the process resulting from the interaction of the loaded material. For example, in the case of using the catalyst together with 400 mmol Coma described in example 8, noted the following e is 8% CO2(the rest is H2and, 2:1), there was a 20% decrease of catalytic activity; (2) when using synthesis gas (52,73 kg/cm2containing 26% N2THAT 7.4% CO2and 2.5% H2S (the rest is H2and, 2:1), the productivity of the process is reduced by 50%

Example 24.

In yet another embodiment of the invention 3.0 g of dried zeolite (13-fold quantity dried in vacuum at 400oC for 4 hours) enter in the boot process raw material together with 400 mmol Coma in 100 ml of methanol. The reactor is rinsed with hydrogen, add 5 mmol Ni(CO)4. Lower the pressure in the reactor to 52,73 kg/cm2with the introduction of synthesis gas (H2:/2: 1), and then heated to 110oC. flow rates were 10% higher compared to consumption when using the solutions of a catalyst not containing zeolite. Advantages of using media carbonyl transition metal, such as zeolite, are: (1) absence of methylformate, which is usually present in small quantities as a by-product, and (2) immobilization of Ni(CO)4on the zeolite. The results of IR analysis of the gas phase indicate that the concentration of Ni(CO)H2PCOand the stirrer speed on the reaction rate experiments were carried out with the introduction of 20 servings of raw materials. Table 5 shows the reaction conditions for each test. All the tests were carried out when the initial concentration of Ni(CO)40.05 M, in addition to tests 1 and 2, which used an initial concentration of about 0.01 M Test 21 was performed using methyl ester of formic acid as a solvent with methanol, while in other experiments used either pure methanol or methanol/steam-dioxane as solvent.

The concentration of methanol, the base and Ni(CO)4in the liquid phase, are shown in table 5, calculated from the assumptions that (1) no change in volume occurs when mixing para-dioxane, methanol and KOCH3and (2) any change in the density of the liquid phase does not occur in the interval from 25oTo the reaction temperature. Thus, the concentration of methanol KOCH3and Ni(CO)4more precisely, given as mol/l at 25oC.

Tests 1 and 2 belong to a single experiments using concentrations of Ni(CO)4about 0.01 M, so arenou (not excessive) the reaction rate is defined as the speed for which you want from 2 minutes to 2 hours to reduce the pressure at the beginning of the reaction from 52,73 to 7.03-10,55 kg/cm2. The speed of reaction in tests 1 and 2 is relatively slow and is believed to decrease even when using the interested interval low temperatures. Thus, for all subsequent trials used higher initial concentration of Ni(CO)4. The specified concentration of Ni(CO)4leads to a moderate speed of reaction.

Tests 3 and 5 were conducted to determine the reaction rate in these experiments, in the case of limiting the mass transfer Tests 4, 7, 9 and 11 was carried out at temperatures 116, 70, 98 and 87oWith accordingly in order to clarify the effect of temperature on rate of reaction. In test 6 was attempted repetition of the technique experience 4, but at a slower speed stirrer to determine the rate of reaction when the mass transfer limitation. However, test 6 was completed before it was reached the reaction temperature in accordance with test 4.

Test 8 was the first test conducted in the presence of methanol used in the beginning of the reaction. This test was carried out at 90oWith so is I. The reaction rate at the temperature of 90oWith was slower than expected, because in all subsequent tests, where methanol was present from the beginning of the synthesis, the reaction temperature was maintained at about the level 110oC.

Tests 10, 12 and 13 were performed to determine the effect of methanol on the reaction rate. The initial concentration of methanol used in these experiments were, respectively, 25, 10, and 50. Tests 14, 15 and 16 were also carried out to establish the effect of methanol concentration on the reaction rate at various concentrations of the base catalyst. These tests were carried out at initial concentrations of methanol, 25, 75 and 100 rpm. accordingly, while the initial concentration KOCH3was $ 4.0 M

Test 17, which repeated the test method 15, except that the speed of the stirrer was higher, conducted with the aim of establishing: does the mass transfer rate of the reaction in experiments with higher concentrations of base. Tests 18 and 19, repeating the test method 16, but when using higher concentrations Foundation conducted to establish the effect of base concentration on the flow velocity, PR is 19, but using as the solvent is about 10. methyl ester of formic acid was performed to determine the degree of influence of methylformate on the reaction rate.

Was also conducted another experiment (test 18) to confirm that Ni(CO)4and potassium methylate are not spent entirely in the process of synthesis, and function as catalysts. This test was carried out for 3 days with multiple pressure decrease in the reactor with the introduction of synthesis gas, resulting in the pressure in the reactor was decreased to 14,06 kg/cm2.

Example 26.

In the following example shows the synergistic effect of two-component system in the synthesis of methanol. 1 mmol of Ni(CO)45 mmol of methylate copper and 0.6 mole KOCH3dissolve in 100 ml of methanol. In the reactor creates a low pressure with the introduction of synthesis gas (H2:/2:1) followed by heating to 120oC. the Methanol obtained when the gas flow rate is about 0,352 kg/cm2/min.

Example 27.

5 mmol of Ni(CO)4added to a solution containing 0.4 mole of Coma, dissolved in a mixture of 30% methanol and 70% triglyme (dimethylaminophenol), and then in the reactor lower the pressure to 52,73 kg/cm2oC.

Example 28 using a Ni/Mo-system.

A mixture of Nickel acetate (10 mmol), hexacarbonyl molybdenum (5 mmol) and 100 mmol of tert-Aminata sodium is heated in 100 ml of tetrahydrofuran under pressure 21,09 kg/cm2synthesis gas (H2:/2:1) at 100oC. the gas Flow rate is 0.14 kg/cm2/min and get 87 mmol of methanol.

Example 29 using a Ni/Co system.

When heated mixture containing 8 mmol of Nickel acetate, 2 mmole of cobalt acetate, 100 mmol of tert-Aminata of sodium in 100 ml of tetrahydrofuran under 100oWhen the pressure 21,09 kg/cm2synthesis gas, and after 2 additional downloads at pressure 21,09 kg/cm2each synthesized Meon is 163 mmole. The gas flow rate is 0.13, and 0.25, 0.21 kg/cm2/min at downloads 1,2,3 respectively.

Example 30 using a Ni/Cu system.

Add 7 mmol of Ni(OAc)2, 3 mmole si(SLA)2and 100 mmol of trilaminate sodium to 100 mmol of tetrahydrofuran and heated the mixture at 100oWhen the pressure 21,09 kg/cm2the synthesis gas. When 3 consecutive downloads the gas flow is of 0.07, and 0.04, 0.12 kg/cm2/min, respectively. Get 36 mmol Meon. Under these conditions, Ru and Pd no reason Coma, 300 mmol Meon and 108 ml triglyme and heats them in 120oWhen the pressure 21,09 kg/cm2(H2:/2: 1). 120 mmol of H2and 170 mmol spent WITH education up to 60 mmol Meon. An additional issue is to obtain a by-product of methylformate.

Example 32 using With the system.

10 mmol of Co(SLA)260 mmol of tert-Aminata of sodium and 100 ml of tetrahydrofuran is heated at a temperature of 100oWhen the pressure 21,09 kg/cm2synthesis gas (H2:/2: 1). The pressure decreases and after 260 minutes, the reactor is cooled. Get 16 mmol Meon during the reaction.

Example 33 using the MIS system.

Heat 5 mmol of Mo(CO)6, 120 mmol Coma, 300 mmol Meon and 108 ml triglyme at 150oWhen 53,43 kg/cm2synthesis gas (H2:/2:1). The gas flow rate is 0.05 kg/cm2112 mmol CO and 106 mmol N2respectively to 53 mmol Meon.

Example 34.

60 mmol of tert-Aminata potassium, 25 ml of tert-butyl alcohol as a solvent, and 5 mmol of tetracarbonyl Nickel loaded into a Parr reactor with a capacity of 300 ml, and the contents are mixed and heated under pressure (21 kg/cm2) synthesis gas (H2:/2:1) at a temperature of 1002. A total of three downloads give 124 mmole Meon.

Example 35.

System EN3(CO)12/KOMe experience in the dimethyl ether of triethylene glycol as the primary solvent without the addition of methanol. The pressure decreases from 69,51 to 60,55 kg/cm2after 22 minutes at a temperature of 150oC. the Final pressure is 4,046 kg/cm2at 25oC. the Reaction was very slow, as the gas flow rate is dropped to 0.07 kg/cm2/min. and the resulting solution was dark brown liquid containing 20 mmol Meon.

In this system it is possible to use dimethyl ether of tetraethyleneglycol instead of the dimethyl ether of triethylene glycol.

Literature

1. U.S. patent N 4590216, CL 07 From 27/08, 1986.

2. U.S. patent N 4731386, class C 07 C 27/06, 1988.

3. U.S. patent N 4476334, class C 07 C 20/00, 1984.

4. U.S. patent N 4301253, class C 07 C 27/06, 1981. TTT TTT TTT TTT

1. Homogeneous catalyst for synthesis of methanol from carbon monoxide and hydrogen at low temperatures and pressure, contain the complex of the transition metal carbonyl, ALCOHOLATES component, the solvent is methanol, the organic co-solvent, characterized in that as a carbonyl complex of a transition Nickel, cobalt, molybdenum, ruthenium or mixtures thereof, as ALCOHOLATES component - alcoholate of the General formula AM-OR, where AM Na+, K+N(Me+)4, OR derived FROM1-C5aliphatic alcoholate, in the following ratio of components, mmol:

The complex of the transition metal carbonyl 1-20

Alcoholate component of the above groups 40-800

The carbonyl complex of the transition metal /AM or SIG-ratio 2-800

The solvent is methanol Not more than 2500

The co-solvent is Not more than 1500

2. The catalyst p. 1, wherein the transition metal is selected from the group consisting of Nickel, molybdenum and copper.

3. The catalyst p. 1, characterized in that the transition metal used Nickel.

4. The catalyst p. 1, characterized in that as a co-solvent use solvent selected from the group of tetrahydrofuran, paradoxine, treuillage alcohol, butyl alcohol and glycols.

5. The catalyst p. 1, characterized in that the carbonyl complex of the transition metal is a complex of tetracarbonyl Nickel, as alcoholate use methylate and the catalyst solution is audica fact, as a carbonyl complex of a transition metal is used, the complex of tetracarbonyl Nickel, as alcoholate use methylate and the catalyst dissolved in the cosolvent system consisting of methanol and paradoxine.

7. The catalyst p. 1, characterized in that as a complex of transition metal carbonyl use complex tetracarbonyl Nickel, as the alcoholate methylate, and the catalyst dissolved in the cosolvent system consisting of methanol and glycol, its dimethyl ether, dimethyl ether, triethylene or tetraethyleneglycol.

8. A method of producing a catalyst for synthesis of methanol from carbon monoxide and hydrogen at low temperatures and pressures by the interaction of the carbonyl transition metal or its predecessor with a reagent which forms the alcoholate in the presence of a system of methanol with organic co-solvent, characterized in that the interaction is performed with the use of the carbonyl transition metal or its predecessor metal selected from the group comprising copper, Nickel, cobalt, molybdenum, ruthenium or mixtures thereof, as a reagent, forming the alcoholate ion Spolsky solvent, selected from the group comprising tetrahydrofuran, paradoxon, dreamily alcohol, polyethylene glycol, and dimethyl ether of polyethylene glycol.

9. The method according to p. 8, characterized in that the reagent on the basis of transition metal carbonyl use tetracarbonyl Nickel, and as a reagent, giving the alcoholate ion, use aliphatic C1-C5the alcoholate of an alkali metal.

10. The method according to p. 9, characterized in that as an alcoholate of an alkali metal use potassium methylate.

11. The method according to p. 8, characterized in that the anion of the amino compounds used methylate Tetramethylammonium.

12. The method according to p. 8, wherein the alcoholate get ie mixture of potassium methylate and methylate copper, which leads to the creation of the methylate ions and the formation of complex tetracarbonyl Nickel carbonyl copper.

13. The method according to p. 8, characterized in that the system is solvent with methanol consists of methanol and co-solvent.

14. The method according to p. 8, characterized in that the reagent-based carbonyl transition metal is injected media.

15. The method according to p. 14, characterized in that as the carrier is used zeolite.

in p. 16, characterized in that the interaction is carried out in the regime of low temperatures, in the range from 100 to 150oWith low pressure from 7,03 to 10,55 kg/cm2.

20. The method according to p. 16, characterized in that as a complex of transition metal carbonyl use complex tetracarbonyl Nickel, as the alcoholate methylate, which is produced from potassium methylate, and as a solvent using methanol and co-solvent selected from the group consisting of tetrahydrofuran, paradoxine, polyethylene glycol and the dimethyl ether of triethylene glycol or dimethyl ether tetraethyleneglycol.

21. The method according to p. 16, characterized in that the reaction solution is injected activator carbonyl transition metal.

22. The method according to p. 16, characterized in that the reaction solution is injected inactivator, which inactivates the cation associated with the alcoholate.

23. The method according to p. 22, characterized in that as inactivator use polyethylene, which reacts similarly crown-ethers.

24. The method according to p. 16, characterized in that the synthesis gas may contain inert gases.

25. The method of synthesis of methanol from gaseous reactants CO and H2under item 16, distinguish the 3 with the subsequent introduction of CO and H2when the initial pressure of approximately 52,73 kg/cm3and the final pressure of approximately 8,08 kg/cm3by introducing paradoxine as a co-solvent CH3IT is for translation of the catalyst in the liquid phase and the release of methanol from the resulting product.

 

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