Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
  • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
  • B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C68/00—Preparation of esters of carbonic or haloformic acids
  • C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
  • B01J2531/16—Copper

Definitions

• the invention relates to a process for the preparation of dialkyl carbonates, a copper-containing catalyst and the use of a copper-containing catalyst according to the invention.
• Dialkyl carbonates are industrially important compounds which find application in various fields. Some members of this class of compounds, such as dimethyl carbonate, are low toxicity intermediates that can replace toxic intermediates, such as phosgene or dimethyl sulfate, in many reactions. Another advantage is that they are not corrosive and In addition, no environmentally harmful by-products arise when using them. Because of these properties, dialkyl carbonates are of great importance in the chemical industry for a variety of syntheses. Dimethyl carbonate can be used to improve the octane rating of gasoline and thus replace environmentally problematic lead compounds. In addition, it can be used as a non-toxic and biodegradable solvent.
• MeO ' OMe A further disadvantage is that the catalysts lead to corrosion of the reactor and that the catalyst is deactivated by water, which is formed as a by-product in the reaction.
• ENICHEM process of oxidative methanol carbonylation are summarized in a review article [N. Keller, G. Rebmann, V. Keller, J. Mol. Cat. A 2010, 317, 1].
• the BAYER company describes a process in which a hydrophilic electrolytic inorganic salt melt of KCl and CuCl is used as a catalytic solvent [Z. Kricsfalussy, H. Waldmann, H.-J. Traenckner (BAYER), EP 0 636 601 A1, 1995 and Z. Kricsfalussy, H. Waldmann, H.-J. Traenckner, Ind. Eng. Chem. Res. 1998, 37, 865.].
• the catalytic solvent (KCl / CuCl melt) is placed in a reactor vessel.
• the educts are fed via a gassing stirrer as gas.
• the actual reaction product dimethyl carbonate forms an azeotropic mixture with the by-produced water, which is distilled out of the reactor vessel. In this way, the water can be at least partially separated and a deactivation of the catalyst can be limited by water.
• the method has the disadvantage that the reaction water can not be completely separated by the distillation as an azeotrope with DMC and therefore accumulates with increasing reaction time in the hydrophilic salt melt.
• the water content in the molten salt is brought to a considered advantageous water content of less than 10 wt.%.
• this is only possible at high temperatures of 120 - 300 ° C.
• these conditions lead to the hydrolysis of DMC to CO2 and thus to a poor CO selectivity or to a bad one
• a particular characteristic of the said process is the implementation of a heterogeneous gas-solid reaction in which the starting materials and products are in the gas phase, while the catalyst is present in the solid phase.
• the advantage of heterogeneous process management lies in the fact that the Catalyst and by-produced water are not in the same phase. By this configuration, the deactivation of the catalyst can be limited by the water.
• Another advantage of using a two-phase system is the easier product separation.
• a serious disadvantage is that a diffusion of the reactants to each other and in particular to active centers within the solid catalyst phase due to physical laws is very limited. In addition, only a limited solubility of the educts in the solid catalyst phase. Of the total, in the solid catalyst phase, active catalyst sites active only those are efficiently used, which are arranged on the catalyst surface. This reduces sales.
• a further disadvantage is that in the process mentioned a creeping deactivation of the solid catalyst with a reactivation of the catalytic centers must be countered by organohalogen compounds. This complicates the process and leads to an increase in costs.
• this method has the disadvantage that it is carried out homogeneous catalysis in a methanol solution.
• the water accumulation in the hydrophilic catalyst phase leads to the above with increasing reaction time to deteriorating CO and product selectivity and thus to a low yield.
• the separation of product and catalyst in homogeneous processes is extremely complicated and costly. Due to the toxicity and combustibility of methanol, the process is associated with a relatively high risk potential and therefore requires special safety measures. The use of the solvent is therefore associated with a cost.
• the object of the invention is therefore to overcome these and other disadvantages in the prior art and to provide a catalytic process for the preparation of dialkyl carbonates available, which overcomes the disadvantages of known methods and provides the highest possible dialkyl carbonate yield.
• the method should have the lowest possible risk and also allow easy and rapid separation of the reaction product from the catalyst.
• the process should be simple to perform and inexpensive to use.
• the catalysts should also allow high conversion rates in the absence of a solvent.
• Catalysts supported on solid phases are particularly easy to separate from further constituents of a reaction mixture. Due to their easy separability, additional purification steps, such as extraction or chromatography, are eliminated, especially during product recovery. Consequently, with the aid of the support, both the expenditure of time and the amount of material required in the method can be significantly reduced.
• the application of the copper-containing catalyst to a porous support significantly increases the surface area of the catalyst phase and thus the exchange surface between the catalyst phase and the educts and products which is available during the reaction. In this way, in the process with a simple means very high reaction rates and thus high conversions can be achieved.
• the supported catalyst can be introduced into a fixed bed reactor and used, for example, in a continuous process.
• the known advantages of a continuous reaction such as improved reaction control, smaller reaction volume, small space requirement of the reactor, etc. can be used.
• Suitable support materials are particularly porous inorganic and organic substances.
• Suitable inorganic carriers are SiO 2 , Al 2 O 3 , zeolites and carbon.
• Suitable organic support materials are polymers such. B. polystyrene.
• Vankelecom P.A. Jacobs, Adv. Synth. Catal. 2006, 348,, 1413; N.E. Leadbeater, M. Marco, Chem. Rev. 2002, 102,, 3217.).
• the liquid catalyst phase With the aid of the liquid catalyst phase, it is possible in an advantageous manner to provide a means in multiphase systems which additionally promotes the discharge of the water from the catalyst phase into an educt / product phase.
• the polarity of the catalyst phase is made such that a hydrophobic character results, due to which the discharge of the water is forced.
• the copper-containing catalyst, or an additive contained in the liquid catalyst phase have a hydrophobic or lipophilic character.
• the liquid catalyst phase can consequently be used to ensure, with a comparatively simple means, that the process according to the invention gives a high conversion even in the case of long transit times. Due to the polarity, the transverse solubility can also be influenced in multiphase continuous systems.
• the process uses a copper-containing catalyst which is present in a liquid catalyst phase also provides an important prerequisite for achieving high diffusion rates between the catalyst phase and the reactants and products in the process. you can. In this way, the reactants can easily diffuse into the liquid catalyst phase and be reacted there quickly with the aid of the catalyst, so that high conversion rates can be achieved in the process.
• the process according to the invention can also be carried out in a 3-phase system with a gaseous educt / product phase. It is also particularly advantageous because with a suitable choice of process conditions, the by-produced water is gaseous.
• the catalyst comprises a copper-containing coordination compound.
• a coordination compound in the context of the invention includes both neutral complexes and the salts of cationic and anionic complexes. Copper-containing coordination compounds have proven to be very efficient catalysts in the preparation of dialkyl carbonates and.
• the copper-containing coordination compound has a melting point of less than 120 ° C, preferably less than 15 ° C, more preferably less than 100 ° C and most preferably less than 80 ° C. This is particularly advantageous because the process can thereby be carried out even at relatively low temperatures, without the use of a solvent for providing the catalyst phase liquid under process conditions is necessary. This property thus provides an important prerequisite for the entire process to be carried out in the absence of a solvent.
• Solvents are often toxic and / or flammable, so their use is usually associated with an increase in the hazard potential of a process. Furthermore, the use of solvents has a negative impact on the atom economy of a production process and is therefore associated with increased process costs. In a solvent-free implementation of the method, this can be avoided. The possibility of such a procedure is therefore particularly attractive.
• the at least one copper-containing coordination compound forms the liquid catalyst phase.
• the copper-containing coordination compound contains at least one nitrogen (III) compound as AADonorligand and / or a quaternized nitrogen (III) compound as an organic cation, wherein the nitrogen (III ) - compound is selected from the group of A / -Alkylimidazolen, N, N-dialkylaminopyridines, AAAlkylpyrazolen or AAAlkyl-pentaorganoguanidinen.
• This embodiment is particularly advantageous since the said copper-containing coordination compounds provide particularly good results in processes for the preparation of dialkyl carbonates by catalytic oxidative carbonylation of an alcohol.
• the Lewis acidity of the copper-containing catalyst can be reduced. Reducing the Lewis acidity limits the ability of the catalyst to also catalyze the undesired hydrolysis of the dialkyl carbonate. By this configuration, therefore, the selectivity of the catalytic reaction can be increased and thus the efficiency of the process can be increased.
• the copper-containing co-ordination compound contains at least one A / -alkylimidazole as AADonorligand and / or a quaternized A / -Alkylimidazol, i. an A / alkylimidazolium ion, as an organic cation.
• the copper-containing coordination compound has at least one lipophilic substituent. It is advantageous, in particular, that a lipophilic substituent, such as e.g. a long alkyl substituent can be provided very easily and because of its polarity is suitable for promoting the discharge of the water from the catalyst phase. In this way, the deactivation of the catalyst can be counteracted.
• the lipophilic substituent is preferably an aliphatic substituent having a number from 1 to 25 carbon atoms, and most preferably an alkyl substituent having from 1 to 25 carbon atoms.
• the lipophilic substituent may have substituents such as e.g. Have alkyl chains.
• an advantage of this embodiment is in particular that the lipophilic substituent is located on a component of the catalyst, thereby directly counteracting deactivation of the catalyst by water.
• a particularly important embodiment provides that the lipophilic substituent is provided on the nitrogen (III) compound. It is furthermore preferred that the lipophilic substituent is arranged on the nitrogen of the nitrogen (III) compound. With this embodiment, particularly high yields could be achieved in processes for the preparation of dialkyl carbonates.
• a further advantage is that the melting point of the coordination compounds can often be lowered by the introduction of the lipophilic substituent, especially in the case of copper-containing coordination compounds which have at least one A / -alkylimidazole.
• a copper-containing coordination compound can be readily provided which is liquid under process conditions.
• a preferred embodiment of a method according to the invention also provides that gaseous starting materials are brought into contact with the catalyst phase, and that the products are removed via the gas phase.
• a product is water.
• the catalyst is an ionic liquid, wherein the copper-containing coordination compound is contained in the anion and / or in the cation of the ionic liquid. This is particularly suitable since particularly good dialkyl carbonate yields could be achieved with processes designed in this way.
• Ionic liquids are salts that already melt at a temperature of ⁇ 100 ° C. They are usually composed of an organic cation and an organic or inorganic anion. They are characterized by a number of advantageous properties. For example, they are not inflammable, have a very low vapor pressure and also have very good dissolution properties. In this way it can be ensured that the educts used in the process are soluble in the catalyst phase. A further advantage is that ionic liquids have a low melting point and often also a relatively high thermal stability. Thus, the method according to the invention can be carried out in a wide temperature range.
• dialkyl carbonate yields can also be achieved in that the anion of the ionic liquid is either a copper-containing coordination compound or from [CuCl 2 ] - , [CuBr 2 ] - , [Cul 2 ] - , [BF 4 ] " and [PF 6 ] "is selected.
• the copper-containing coordination compound is selected from the ionic liquids [Cu (Im 12 ) 4 ] [PF 6 ], [Cu (Im 12 ) 2 ] [CuCl 2 ], [Cu (Im 12 ) 2 ] [CuBr 2 ], [Cu (lm 6 ) 2 ] [CuCl 2 ], [Cu (lm 6 ) 2 ] [CuBr 2 ], [DMIM] [CuCl 2 ], [DMIM] [CuCl 2 ] [DMIM] 2 [CuCl 3 ],
• An important embodiment of the process provides that branched and unbranched alkanols having 1 to 4 carbon atoms are reacted. Very particular preference is given to the catalytic oxidative carbonylation of methanol to dimethyl carbonate.
• An important embodiment provides that the process in a temperature range of 60 ° C to 200 ° C, preferably from 70 ° C to 140 ° C, more preferably from 75 ° C to 120 ° C and most preferably from 80 ° C to 1 15 ° C is performed. Especially at temperatures below
• the process is carried out as a continuous process. Continuous synthesis runs are known.
• a method according to the invention can be based on all of the known execution protocols.
• the catalyst can be placed in a fixed bed reactor which is separate from the remainder of the reaction mixture, i. is continuously flowed through by the reacted alcohol, the carbon monoxide and the oxygen.
• a particularly advantageous development provides that the continuous process is carried out in the gas phase.
• an additive is contained in the liquid catalyst phase.
• the additive can advantageously be used to optimally match the physical properties such as the viscosity of the catalyst phase or the starting material solubility (in particular the solubility of the alkanol) to the process conditions.
• the additive is preferably a low-volatility compound such as, for example, a silicone oil or a perfluorinated polyether oil.
• a particularly preferred process for the preparation of dialkyl carbonates provides that the catalyst is applied to the solid phase support by non-covalent interaction. It is advantageous here that in the preparation of the catalyst used in the process, the attachment of this to the solid phase carrier is eliminated.
• the support of the catalyst is thus comparatively simple. In contrast to a covalent support, in the case of a non-covalently supported catalyst, no special linker for the application of the catalyst to the solid phase support has to be introduced. This reduces the cost of producing the catalyst and thus the cost of the entire process.
• the solid phase support is formed by SiO 2 .
• SiO 2 is a low-cost carrier material that is available in many different designs in terms of its shape, its particle size and its surface finishes.
• the support material can also be used in a wide temperature range.
• the solid-phase support of SiO 2 is formed with a particle size between 0.05 mm and 4 mm and a BET surface area of 250 to 1000 m 2 / g.
• a solid phase support of SiO 2 which has a particle size between 0.063 mm and 0.2 mm and a BET surface area of 300 - 400m 2 / g.
• the process uses a copper-containing catalyst supported on a solid phase support, in which the mass ratio of the copper-containing catalyst to the solid phase support is between 0.075 and 1, 350, more preferably between 0.150 and 0.750, and most particularly preferably between 0.300 and 0.590.
• the invention further provides a copper-containing catalyst which is supported on a solid phase support and which is present in a catalyst phase which has a melting point of less than 120 ° C., and which contains at least one copper phase.
• the copper-containing coordination compound contains at least one nitrogen (III) compound as AADonorligand and / or a quaternized nitrogen (III) compound as an organic cation, wherein the nitrogen (III) compound is selected from the group of A / alkylimidazoles, A /, A / dialkylaminopyridines, AAalkylpyrazoles or AAalkylpentaorganoguanidines.
• the copper-containing catalyst is supported on a solid phase support and is present in a catalyst phase containing a
• a catalyst can be provided, which can be particularly easily separated from further components of the reaction mixture when using the catalyst in a catalytic process.
• the application of the copper-containing catalyst to a porous support significantly increases the surface area of the catalyst phase and thus the exchange surface between the catalyst phase and the educts and products which is available during the reaction. In this way, when using a catalyst according to the invention in a catalytic process very high reaction rates and thus high conversions can be achieved.
• a further advantage is that a liquid catalyst phase is provided in a catalyst according to the invention. This can provide an important prerequisite for achieving high rates of diffusion between the catalyst phase and the starting materials and products. Infol- The educts can readily be diffused into the liquid catalyst phase and reacted there quickly with the aid of the catalyst, so that high conversion rates can be achieved when using a catalyst according to the invention in a catalytic reaction.
• the fact that the copper-containing catalyst is present in a catalyst phase having a melting point of less than 120 ° C also provides an important prerequisite for the catalyst to be used in a process in which the catalytic reaction is already takes place at relatively low temperatures even in the absence of a solvent in a liquid phase.
• Solvents are often toxic and / or flammable, so that their use is usually associated with an increase in the hazard potential of a process. Furthermore, the use of solvents has a negative impact on the atom economy of a process and is therefore associated with increased costs. In a solvent-free reaction, this can be avoided. A catalyst that makes this possible is therefore particularly attractive.
• the catalyst phase has a melting point of less than 120 ° C, preferably less than 15 ° C, more preferably less than 100 ° C and most preferably less than 80 ° C.
• the melting point of the liquid phase the lower the temperatures, the catalyst can be used without the addition of a solvent in the liquid phase.
• the copper-containing coordination compound has a melting point of less than 120 ° C, preferably less than 15 ° C, more preferably less than 100 ° C and most preferably less than 80 ° C.
• a catalyst phase can be particularly easily se, which has a melting point less than 120 ° C, or less than 15 ° C, less than 100 ° C or less than 80 ° C.
• the catalyst has at least one lipophilic substituent. This is particularly advantageous since the introduction of the lipophilic substituent can influence the melting point of the catalyst.
• a further advantage is that the polarity of the catalyst can be adapted to its intended use by the lipophilic substituent.
• the lipophilic substituent can reduce the transverse solubility in the polar phase. In this way, detachment of the catalyst from the solid phase support or removal of the catalyst from the catalyst phase can be prevented.
• the lipophilic substituent is preferably an aliphatic substituent having a number from 1 to 25 carbon atoms, and most preferably an alkyl substituent having from 1 to 25 carbon atoms.
• the lipophilic substituent may itself also have substituents such as e.g. Have alkyl chains.
• a particularly important embodiment provides that the lipophilic substituent on the nitrogen (III) compound is provided. This is particularly advantageous because catalysts constructed in this way often have a melting point of less than 120.degree.
• the catalyst is an ionic liquid, wherein the copper-containing coordination compound is contained in the anion and / or in the cation of the ionic liquid.
• Ionic liquids in which the copper-containing coordination compound is contained in the anion and / or in the cation of the ionic liquid and in particular those in which the copper-containing coordination compound at least a least one A / -Alkylimidazol as AADonorligand and / or a quaternized N-alkylimidazole as an organic cation, generally show a high thermal stability. This is particularly advantageous, since even with long reaction times, no decomposition of the catalyst takes place, so that the process yields constant conversions.
• a particularly high thermal stability could be achieved also if the anion of the ionic liquid represents either a copper-containing coordination compound or from [CuCl 2] ⁇ , [CuBr 2] ⁇ [Cul 2] ⁇ , [BF 4] "and [ PF 6 ] " is selected.
• catalysts according to the invention it is also possible to influence the properties (for example reactant solubility, flow properties) of the catalyst phase by adding further, low-volatility components.
• these components such as Silicone oils and perfluorinated polyether oils are mixed with the catalytically active liquid prior to application of the liquid film to the support and then applied to the support material, if appropriate with the aid of a solvent.
• the catalyst is applied by noncovalent interaction to a solid phase support.
• the solid phase support of the catalyst is formed by SiO 2 .
• SiO 2 is a low-cost carrier material that is available in many different particle sizes and surface finishes. The support material can also be used in a wide temperature range, this has an advantageous effect on the applications of the catalyst.
• the solid phase support is preferably formed by SiO 2 having a particle size between 0.05 and 4 mm and a BET surface area of 250 to 1000 m 2 / g. Particularly preferred is a support of SiO 2 having a particle size between 0.063 - 0.2 mm and a BET surface area of 300 - 400m 2 / g.
• the mass ratio of the copper-containing catalyst to the solid phase support is between 0.075-1.350 and more preferably between 0.150-0.750 and very particularly preferably between 0.300-0.590.
• the copper-containing coordination compound is selected from the ionic liquids
• the invention additionally provides for a use of a catalyst according to the invention in an oxidative carbonylation. This is particularly advantageous since the catalysts according to the invention have led to particularly high conversions when used in such reactions.
• the catalysts according to the invention are particularly suitable for such an application since they have, on the one hand, a copper complex and, on the other hand, high thermal stability. Oxidative carbonylations can be catalyzed by copper complexes. In addition, these reactions are also often carried out at elevated temperatures.
• a catalyst according to the invention in an oxidative carbonylation of alkanols in the presence of oxygen is particularly preferred. and carbon monoxide to dialkyl carbonates.
• very particular preference is given to the use of a catalyst according to the invention in an oxidative carbonylation of branched and unbranched alcohols having 1 to 4 carbon atoms to form dialkyl carbonates.
• good results could be achieved with the ionic liquids according to the invention in the oxidative carbonylation of methanol to dimethyl carbonate.
• a particularly simple process for the preparation of the catalyst according to the invention provides that either the copper-containing coordination compound itself, or in an in situ preparation of these, the components required for the preparation of the copper-containing coordination compound under inert gas and optionally at elevated Temperature and / or be applied with shaking and / or the action of ultrasound on the solid phase support.
• a solvent which forms a solution with the corresponding component (s) of the catalyst. Solvents such as acetonitrile, methanol, tetrahydrofuran or dichloromethane are particularly well suited for this purpose.
• the solid phase carrier is treated with an excess of said solution. After the mass transfer between the solid phase support and the solution, the excess solution is removed.
• Another method is the spraying of the solid phase carrier with such a solution.
• an added solvent is removed during or after the spraying process.
• the catalyst supported on a solid phase support is preferably prepared by displacing the solid phase support with a solution of the catalyst or, in the case of an in situ preparation with a solution of the corresponding components, in a solvent and then evaporating off the solvent.
• Fig. 1 is a schematic representation of a continuous gas phase reactor.
• FIG. 1 shows a schematic representation of a continuous gas-phase reactor.
• a continuous gas-phase reactor Such a reactor was used to carry out the continuous processes described in the working examples in Table 3.
• the metering of the gases takes place via mass flow controller 1.
• the system pressure is set at the pressure control valve 7.
• the liquid educt (in a reaction according to Table 3, methanol) is conveyed via an HPLC piston pump 2 and brought in a heated evaporator 3 in the gaseous state.
• the fixed bed reactor 4 is a stainless steel pipe. If required, the volumetric flow of the reaction gases can be passed through a second, identically constructed reactor 5 or via a bypass 6 past the reactor. All pipelines of the experimental apparatus are electrically heatable.
• the products are detected by an online gas chromatograph 8 with Restek RTX-5 column and flame ionization detector.
• Crystals of I suitable for single crystal structure analysis were obtained from MeOH at room temperature, taken up in inert oil, and transferred to the cold N 2 cooling gas stream of the diffractometer. 1 .2 [Cu (lm 12 ) 2 ] [CuCl 2 ] (II)
• IR (substance) ⁇ ' 3122, 3051 w, 2949, 2916vs, 2847s, 1690w, 161v, 1533, 1520, 1466, 1442, 1399w, 1375, 1357, 1288, 1255w, 1240, 1 1 10s, 1053, 1039, 1026, 1006w, 962, 890w, 845, 833, 757vs, 730, 721, 654s, 630, 506w, 444w and 428w.
• IR (Substance) v - / cm -3 ' 3122, 31 12, 3049w, 2949, 2916vs, 2847s, 1685w, 1608w, 1533, 1520, 1465, 1442, 1397w, 1376w, 1341w, 1288, 1255w, 1239, 1 1 10, 1 100, 1053w, 1039w, 1026w, 960w, 889w, 843, 832, 755s, 728, 722, 654s, 630, 505w, 444w and 427w.
• Crystals of III suitable for single crystal structure analysis were prepared from CH 3 N / Et 2 O at -20 ° C., taken up in inert oil and transferred to the N 2 cooling gas stream of the diffractometer 1 .4 [Cu (Im 6 ) 2 ] [CuCl 2 ] (IV)
• 1-hexylimidazole (Im 6 ) (4.84 g, 31.8 mmol) was added to CuCl (2.97 g, 30.00 mmol).
• the reaction mixture was mixed with CH 3 CN (5 ml) for homogenization and sonicated for about 10 minutes.
• the solvent was removed in vacuo and the viscous liquid was digested with ether. After phase separation, the ether phase was decanted.
• Ci 8 H 32 CuN 4 calculates 367.1 91 7); m / z (ESI, negative mode, CH 3 CN)
• Ci 8 H 32 CuN 4 calculates 367.1 91 7); m / z (ESI, negative mode, CH 3 CN)
• Schirenk tube was added to CuCl (200 mg, 2.02 mmol) a solution of [DMIM] Cl (869 mg, 3.03 mmol) in CH 3 CN (5 mL). The reaction mixture was sonicated at room temperature for about 10 minutes. After removal of the solvent in vacuo and freeze drying of the greyish
• CD 3 CN 14.4 (CH 3 (17)), 23.3, 26.6, 29.6, 30.0, 30.2, 30.3, 30.6, 32.6 (CH 2 ( 7-16)), 37.0 (CH 3 (18)), 50.5 (CH 2 (6)), 123.2 (CH (5)), 124.6 (CH (4)) and 136, 8 (CH (2)); m / z (ESI; CH 3 CN) 251, 2480 (. [C 6 H 31 N 2] ⁇ 100% C 6 H 31 N 2 calculates 251, 2482); m / z (ESI, negative mode, CH 3 CN) 222.7651 ([CuBr 2 ] ⁇ 23%, CuBr 2 calculates 220.7648), 264 (35) and 314 (23).
• an ultrasound head is immersed in the water bath and operated at a frequency of 2 s -1 After 15 minutes, a vacuum pump is connected to the flask and the pressure is slowly reduced from 10 5 Pa to 5 * 10 2 Pa. After about 45 minutes a turquoise powder in front, which turns dark green when suddenly in contact with air.
• the suspension is heated in a water bath with stirring to 50 ° C.
• an ultrasound head is immersed in the water bath and operated at a frequency of 2 s -1
• a vacuum pump is connected to the flask and the pressure is slowly reduced from 10 5 Pa to 5 * 10 2 Pa. After about 45 minutes a blue powder before, which discolored suddenly dark green in contact with air.
• an ultrasound head is immersed in the water bath and operated at a frequency of 2 s -1 After 15 minutes, a vacuum pump is connected to the flask and the pressure is slowly reduced from 10 5 Pa to 5 * 10 2 Pa. After about 45 minutes a bluish powder, which suddenly turns dirty green on contact with air.
• the weighing of the unsupported copper (II) compound takes place outside of an inert gas box.
• 6.34 g of [CuBr 2 (Im 12 ) 4 ] are weighed into a 500 ml Schlenk flask.
• 90 ml of acetonitrile are added and the mixture is stirred for 15 minutes on a magnetic stirrer.
• 10.52 g of silica gel (particle size 0.063-0.200 mm, BET surface area 335 m 2 / g, pore volume 0.966 ml / g) are added and the suspension is stirred for a further 15 minutes.
• the suspension is heated in a water bath with stirring to 50 ° C.
• an ultrasound head is immersed in the water bath and operated at a frequency of 2 s -1 After 15 minutes, a vacuum pump is connected to the flask and the pressure is slowly reduced from 10 5 Pa to 5 * 10 2 Pa. After about 45 minutes C.
• the reaction apparatus (without reactor) was preheated to 100.degree.
• the copper-containing catalyst was placed in a fixed bed reactor and the fixed bed reactor was screwed into a plant as shown in FIG.
• the heating mantle was placed around the fixed bed reactor and the fixed bed reactor was heated to 100 ° C.
• the volume flow of the reaction gases CO and air was adjusted via two separate mass flow controllers and passed through a bypass (100 ° C) past the fixed bed reactor.
• the volumetric flows were 72 ml / min CO and 51.4 ml / min air.
• the system pressure was set to 5 bar at the pressure control valve.
• Entry 3 of Table 3 shows that increasing the reactor temperature to 120 ° C results in a further increase in the conversion and activity of the catalyst.
• Entry 4 to 7 show that with a further increase in the residence time by increasing the amount of catalyst and increasing the system pressure very significant increases in sales can be achieved.
• the invention is not limited to any of the prescribed embodiments, but can be modified in many ways.

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• 2010
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