Catalytic system for liquid-phase production of methanol from synthesis gas and a method of producing methanol

 

(57) Abstract:

Catalytic system for liquid-phase production of methanol from synthesis gas, containing the following components in a molar ratio of alkali metal methylate to the halide or hydride of copper (1), equal to 7 - 17, modifier selected from the group comprising methylate or an oxide of an element of the group of lanthanum or aluminum oxide, halide or hydride of copper (1), 0.3 - 9,7. The catalytic system further comprises a methylate titanium at a molar ratio of methylate group element lanthanum to methylate titanium, 0.3 to 0.8. A method of producing methanol from synthesis gas in the liquid phase reaction of CO with H2when molar ratio of 0.5 to 5.0 in the presence of the above catalyst system and one or more solvents, to which add the methanol and/or one or more alkylphosphates in such quantity to obtain, in the case of adding methanol, the molar ratio of methanol/Cu between 1 and 500, and in the case of adding alkylphosphate-molar ratio HCOORf/Cu between 1 and 100, if the temperature is above 40oWith and below 200oWith, when the concentration of copper in solution, obtained from solvent and catalyst system, between 0.001 to 1 molar. 2 C. and 16 h. p. F.-ly.

is.

Methanol or methyl alcohol produced on an industrial scale for many decades, has always been valued as an intermediate compound in the chemical industry.

Its characteristic feature is the ability to burn without the emission of pollutants, such as 110x, SOxand dust when used in steam generators or gas turbines, as well as its ability to significantly reduce the release of the SB when used in mixture with gasoline, methyl alcohol makes eco-friendly energy source.

Its use as an energy source is of strategic importance in the sense that it makes possible the utilization of small reserves of natural gas that cannot be used otherwise.

All industrial methods of production of methanol are similar to each other and is based on two main stages, namely, a first stage in which raw materials are converted into synthesis gas, and a second stage in which the mixture(H2)CO2turns into methyl alcohol with a heterogeneous gas-phase catalysis.

Industrial working conditions for the latest generation of copper catalysts is the pressure of 5-10 MPa, a temperature of 230 to 270aboutWith the composition of the gas wanna this, the need to maintain a low content of inertol in the synthesis gas is the main limitation of the existing technology.

Recently developed catalytic system operating under mild conditions of temperature and pressure (90-120about1-5 MPa, respectively). They provide an opportunity to obtain a high conversion WITH above 90% per pass, thus overcome the main limitation of the existing technology. Many of these systems use Nickel as a catalytic metal. Some are in the form of a dispersion of a mixture of the catalyst with the raw materials (US patents N 4614749, 4619946, 4623634), while others use homogeneous catalysis (patent application EP-285228, EP-287151, EP-289067 company Sheii).

All these systems have the disadvantage that under reaction conditions is formed Nickel carbonyl, a very toxic substance. Another system was developed by Mitsui Petrochem Lhd Ltd and does not use Nickel and copper catalysts (Japanese patent application iP 110631/81, iP-128642/82).

Catalytic system for iP 128642/82 characterized by the presence of copper compounds, mainly alcoholate copper, aryloxides copper, copper halides, carboxylates and copper hydrides of copper together with the alkali metal alcoholate, preferably sodium methylate.

Despite the fact that this catalytic system shows interesting features: it has limitations, associated with low productivity, which are the drawbacks from a practical point of view.

It was also found that the catalytic system for the production of methanol can act with greater activity, if made certain additives methanol and/or alkylboron ester of formic acid, preferably of methylformate (see EP-375071 ot SNAMP-ROCEV s.p.A).

It has been unexpectedly found that the addition of one or more of the alcoholate group metals lanthanum and/or adding one or more inorganic oxides of the group of lanthanum and/or aluminum is possible in the presence of one or more of the alcoholate group titanium, if there is at least one alcoholate group of lanthanum, gives catalytic system, which produces methanol, significantly more activity.

The activating effect of lanthanides on the system for hydrogenation WITH has already been addressed in homogeneous catalysis with ruthenium systems (US-4590216 of Union Crbide Corp.) and in heterogeneous catalysis (Cowen et al, Appi atal. 33, 1987, 405) with Ln bimetallic alloys, where the lanthanum is a common element of the lanthanum group.

Both of these systems operate under conditions of temperature and pressure, much otlica described in the application P-128642/82, but in this application it is shown that the titanium alcoholate show a positive effect only in the presence of an alcoholate of the elements of the lanthanum group. The activating effect of the halides of the metals of the group of lanthanum has already been observed (final report DE-as 22-RS Union Corbid Corpto U. S. Department of Energy Jan 1987), but it is less effective than adding alcoholate or oxides, and in some cases may cause false-negative results due to catalyst poisoning by chlorine.

Activating effect of adding inorganic oxides of elements of the group of lanthanum or aluminum has never been documented in systems of this type. It should be noted that the replacement of part of the alcoholate of alkali (or alkaline earth) metal alcoholate of the group of lanthanum (alone or in the presence of an alcoholate group titanium) leads to increased activity remains constant with respect RHO-/SI, where the alcoholate ion RO-connected in accordance with the stoichiometry of metal with the formation of compound (PO)Z, where Z is an alkaline or alkaline earth metal lanthanum or titanium group. However, the catalytic system does not work if the alcoholate of alkali or alkaline earth metal is completely absent.

Co-presence is and using only alcoholate lanthanum group, but significantly cheaper due to the small quantities used derivatives lanthanum group.

The addition of inorganic oxides to the system described in EP-375071, also leads to significantly more active system.

The addition of methanol and/or alkylboron ester of formic acid also causes a significant increase in product yield in the present invention, despite the use of mild reaction conditions.

The number of added methanol and/or alkylphosphate strictly connected with the operating parameters, such as composition of copper, the concentration of the anion, temperature and pressure.

As the reaction conditions and catalyst composition are different, the optimum amount of methanol and/or alkylphosphate that you want to add, also changes, as shown in EP-375071.

However, if the number of added methanol and/or alkylphosphate beyond that listed below, can be obtained negative results.

The next and very important consequence of this amazing fact is that when the transition from batch process to continuous useful part of the methanol must be recyclebank for the system to d of methanol from synthesis gas is characterized by the following: one or more copper compounds; one or more of the alcoholate group elements lanthanum formula (R1xWand/or one or more inorganic oxides of elements of groups landata groups and/or lanthanum and/or group of aluminum; one or more alcoholate of alkaline and/or alkaline earth metals of the formula (RandO)xM; if there is at least one alcoholate lanthanum group, then one or more of the alcoholate group titanium of the formula (RtO)xT, where R1, Raand Rtthat may be the same or equal, this is1-C10is an alkyl group, preferably1-C5is an alkyl group, M is an alkaline or alkaline earth metal; W is an element of the group of lanthanum; T an element of the group titanium; x is the valence of the metal or element; (RaO)xM/CU molar ratio greater or equal to 4, (R1O)xW + (RtO)xT/(RA)xM molar ratio is between 0.01 and 0.3, if there is at least one alcoholate group of lanthanum, and inorganic oxide/S ratio greater 0.5, if there is at least one inorganic oxide of the group of lanthanum or aluminum.

Under the elements of the group of lanthanum refers to elements with atomic number between 57 and 71, but on the Catalyst can be prepared by mixing compounds of copper with alcoholate (and oxides), preferably in an organic solvent, liquid under the reaction conditions.

Copper compounds used in this invention include, for example, carboxylates, as copper acetate, halides, as chloride and copper bromide, alcoholate, as mutilate copper (I) or (II), and copper hydride.

Inorganic oxides are first dried by calcination, and then added to the reaction mixture.

The preferred form described catalytic system consisting of: chloride, copper (I); sodium methylate (CH3ONa); methylate samarium (or lanthanum) (in the presence of methylate titanium or without it) or cerium oxide (or Samaria).

Liquid-phase method for the production of methanol from synthesis gas according to the present invention is characterized by the interaction of CO and H2in the presence of the above catalyst system and one or more solvents, to which is added methanol and/or one or more alifornia formula OORfwhere Rf-C1-C20-alkyl, preferably1-C10-alkyl, and more preferably1is an alkyl group in such quantity to obtain, in the case of adding methanol, the molar ratio methanol/C between 1 and 500 and predpochtitel the flax between 4 and 400, operating at temperatures above 40aboutWith and below 200aboutC, preferably between 60 and 150aboutWith, and when the concentration of copper in solution, obtained from solvent and catalyst system, between 0.001 and 1 molar, and preferably between 0.01 and 0.09 molar.

Preferred is the partial pressure of the reactants is higher than 1 MPa and preferably between 3 and 7 MPa.

Preferred is N2/CO molar ratio of the reaction gases between 0.5 and 5 and preferably between 1.5 and 3.5.

The previously described catalytic system could act in solvent ether type (for example, methyltretbutylether, tetrahydrofuran, normal butyl ether, veratrol, anisole), hard-ether type (glycolic esters, for example, diglyme or tetralin), or ether carboxylic acids (for example, methylisobutyl or butyrolactone).

Other solvents that may be used include sulfones (for example, tetramethylsilane), sulfoxidov (e.g., dimethylsulfoxide) or amines (e.g. pyridine, piperidine or picoline).

The system may also have a high percentage (e.g., 30-60% by volume) of inert compounds, such as N2and is supported above 1 MPa.

This aspect is very important, as it provides a more economical method of preparation of synthesis gas, such as partial oxidation with air.

When working in these optimal conditions should be obtained maximum conversion WITH a pass about 90% when the reaction rate of about 0.06 to S-1(moles of CH3HE obtained per mole of copper per second) and high selectivity to methanol (99%); as side products were observed only dimethyl ether and methylformate.

P R I m e R 1. This example illustrates the implementation of the proposed method in the periodic reactor at 90aboutC and 5 MPa. 3 mmol CUCL, 51 mmol of CH3ONa, 3 mmol Sm(OMe)3, 15 mmol of methanol and 90 ml of anhydrous tetrahydrofuran are mixed in an autoclave at 300 m with a magnetic stirrer. The process is conducted in a nitrogen atmosphere.

The alcoholate of the metals lanthanum group can be easily obtained from the CH3OL and chloride of a metal of the lanthanum group, by way of Metal Alkoxide, S. D. S. Bradiey R. G. Yehrotra, D. P. Caureds, Academic Press, London, 1978).

The reactor is loaded up to 1 MPa with a mixture of CO/H2(1/2 mole), heated to 90aboutS, and the total pressure is then increased to 5 MPa with the same mixture.

Pressure and is, fresh gas is fed continuously to maintain a constant pressure of 5 MPa.

By doing so, after 7 h of reaction get 770 mmol of methanol (excluding the initial number), 144 mmol of methylformate and 1.6 mmol of dimethyl ether.

P R I m m e R 2. Repeats the procedure of example 1, but using instead of Sm(OMe)33 mmol Na(OMe)3.

Acting in accordance with the method of example 1, after 7 h of reaction get 590 mmol of methanol (excluding the initial number), 114 mmol of methylformate and of 1.62 mmol of dimethyl ether.

P R I m e R 3 (comparative). This example demonstrates that the absence of the alcoholate of the elements lanthanum group leads to less active catalytic system.

The process is carried out under the same conditions as in example 1, but without addition of Sm(OMe)3.

Acting in accordance with the method of example 1, after 7 h of reaction get 455 mmol of methanol (excluding the initial number), 95 mmol. methylformate and 2.58 mmol of dimethyl ether.

P R I m e R 4 (comparative). This example demonstrates, if methylate element lanthanum group to be replaced by the same molar amount of the alcoholate ion in the form of MeONa, you will receive less SS="ptx2">

Acting in accordance with the method of example 1, after 7 h of reaction receive 506 mmol of methanol (excluding the initial number), 113 mmol of methylformate and 3.90 mmol of dimethyl ether.

P R I m e R 5. This example demonstrates that the activating effect of the alcoholate lanthanum group is maintained even at a smaller ratio MeO/C.

Served 21 mmol MeONa and 3 mmol Sm(OMe)3that other conditions remain as in example 1.

Acting in accordance with the method of example 1, after 7 h of reaction get 382 mmol of methanol (excluding the initial number), 114 mmol of methylformate and 0.31 mmol of dimethyl ether.

P R I m e R 6 (comparative). This example demonstrates that the addition of lanthanum metal halide groups leads to the system, which is less active than the system containing the alcoholate of a metal of the same group.

Used the same conditions as in example 5, but when loading 3 mmol MeONa and 3 mmol Sml3.

Acting in accordance with the method of example 1, after 7 h of reaction get 56 mmol of methanol (excluding the initial amount) and 14 mmol of methylformate.

P R I m e R 7 (comparative). This example demonstrates that even when the action lower the volumes.

Use the same process conditions as in example 5, but without the addition of Sm(OMe)3and use 30 mmol MeONa.

Acting in accordance with the method of example 1 through 7 h after the reaction receive 336 mmol of methanol (excluding the initial number), 89 mmol of methylformate and 0 mmol of dimethyl ether.

P R I m e R 8. Repeats the procedure of example 5, but instead of Sm(OMe)3added 3 mmol of La(OMe)3.

Acting in accordance with the method of example 1 through 7 h after the reaction receive 361 mmol of methanol (excluding the initial number), 87 mmol of methylformate and 0.15 mmol of dimethyl ether.

P R I m e R 9 (comparative). This example demonstrates that the system cannot operate in the absence of MeONa.

Use the same process conditions as in example 8, but without MeONa and 10 mmol of La(OMe)3.

Acting in accordance with the method of example 1 through 7 h after the reaction receive 8 mmol of methanol (excluding the initial amount) and 3 mmol of methylformate.

P R I m e R 10 (comparative). This example demonstrates that the addition of titanium alcoholate group does not give a more activating effect than an equivalent molar quantity of alcoholate in ademre 1. Acting in accordance with the method of example 1, after 7 h of reaction get 430 mmol of methanol (excluding the initial number), 101 mmol of methylformate and 1.01 mmol of dimethyl ether. This example should be compared with example 4.

P R I m e R 11. This example demonstrates that the addition of small amounts of alcoholate lanthanum group to the titanium alcoholate group leads to a more active system than the system of comparable examples (examples 4, 10).

Loaded 1 mmol Sm(OMe)3and 3 mmol Ti(OMe)4other conditions remain as described in example 1.

Acting in accordance with the method of example 1, after 7 h of reaction receive 621 mmol of methanol (excluding the initial number), 172 mmol of methylformate and 1.69 mmol of dimethyl ether.

P R I m e R 12. This example demonstrates that the presence of titanium alcoholate groups suitable for receiving the active system when using alcoholate lanthanum group.

The process conditions are the same as in example 11, but without the use of Ti(OMe)4.

Acting in accordance with the method of example 1, after 7 h of reaction get 520 mmol of methanol (excluding the initial number), 120 mmol of methylformate and 1.99 is 1 mmol of La(OMe)3instead of Sm(OMe)3.

Acting in accordance with the method of example 1, after 7 h of reaction receive 537 mmol of methanol (excluding the initial number), 137 mmol of methylformate and 1.20 mmol of dimethyl ether.

The following examples demonstrate that the addition of inorganic oxides gives a more activating effect in comparison with the system used in example 4, and the same are claimed in EP-375071.

P R I m e R 14. Using the same reaction conditions as in example 4, with the addition of 2.5 g of Al2O3.

Acting in accordance with the procedure of example 1, after 7 h of reaction receive 594 mmol of methanol (excluding the initial number), 92 mmol of methylformate and of 1.16 mmol of dimethyl ether.

P R I m e R 15. Using the same reaction conditions as in example 4, with the addition of 5 g CEO2.

Acting in accordance with the procedure of example 1, after 7 h of reaction get 780 mmol of methanol (excluding the initial number), 108 mmol of methylformate and of 2.35 mmol of dimethyl ether.

P R I m e R 16. Using the same reaction conditions as in example 4, with the addition of 5 g of La2O3.

Acting in accordance with the procedure of example 1, across delovogo ether.

P R I m e R 17. Using the same reaction conditions as in example 4, with the addition of 5 g Sm2O3.

Acting in accordance with the procedure of example 1, after 7 h of reaction receive 766 mmol of methanol (excluding the initial number), 90 mmol of methylformate and 1.86 mmol of dimethyl ether.

P R I m e R 18. In the autoclave with a capacity of 300 ml, equipped with a magnetic stirrer, download 3 mmol of copper hydride (SYN), 51 mmol of sodium methylate, 3 mmol methylate Samaria, 15 mmol of sodium hydroxide and 90 ml of anhydrous tetrahydrofuran. The process is carried out analogously to example 1 for 7 h, the result 748 mmol of methanol (excluding mmol source of methanol), 149 mmol of methylformate and a 2.01 mmol simple dimethyl ether.

P R I m e R 19. In this example, the source of copper is the copper bromide (3 mmol); all other reaction conditions analogous to example 18.

Through a process similar to example 1, after 7 hours of work received 705 mmol of methanol (excluding mmol source of methanol), 105 millimoles of methylformate and 1.55 mm simple dimethyl ether.

P R I m e R 20. The source of copper in this example is copper iodide (3 mmol), all other conditions analogous to example 18.

P source of methanol), 99 mmol of methylformate and 1.58 mmol simple dimethyl ether.

P R I m e R 21. The source of copper is the copper hydride (3 mmol); all other process conditions analogous to example 18. Get 802 mmol of methanol (excluding the original), 115 mmol of methylformate and 2,69 mmol simple dimethyl ether.

P R I m e R 22. In this example, as an alcoholate of an alkali metal use potassium methylate (51 mmol); all other process conditions similar to example 1.

Implementing technology in example 1, for 7 h are 520 mmol of methanol (excluding mmol source of methanol), 80 millimoles of methylformate and a 7.92 mm simple dimethyl ether.

1. Catalytic system for liquid-phase production of methanol from synthesis gas containing a halide or hydride of copper (I), the alkali metal methylate, characterized in that it further comprises a modifier selected from the group comprising methylate or an oxide of an element of the group of lanthanum or aluminum oxide, in the following molar ratio of the components: methylate alkali metal/halide or hydride of copper (I) 7 17, modifier /a halide or hydride of copper (I) 0,3 9,7.

2. The system under item 1, characterized in that as a modifier with the under item 1, characterized in that as a modifier it contains aluminum oxide or the oxide of the element of the group of lanthanum at a molar ratio of the halide or hydride of copper (I) 4,7 9,7.

4. The system under item 1, characterized in that it further contains methylate titanium at a molar ratio of methylate group element lanthanum to methylate titanium 0,3 0,8.

5. The system under item 2, characterized in that as methylate group element lanthanum it contains methylate samarium or lanthanum.

6. The system under item 3, characterized in that as the oxide of the element groups it contains lanthanum oxide, samarium, cerium or lanthanum.

7. A method of producing methanol from synthesis gas in the liquid phase reaction of CO with H2when the molar ratio of CO/H2from 0.5 to 5 in the presence of catalytic systems based on copper compounds and alkali metal alkoxide and one or more solvents, to which add the methanol and/or one or more alkylphosphates formula

HCOORf,

where RfWITH1WITH20-alkyl,

in this number, to obtain, in the case of adding methanol, the molar ratio of methanol/Cu from 1 to 500, and in the case of adding alkylphosphate molar ratio HCOORf/Cu from the of varicella and catalytic systems, 0.001 to 1 molar, characterized in that the catalytic system contains a halide or hydride of copper (I), the alkali metal methylate and a modifier selected from the group comprising methylate or an oxide of an element of the group of lanthanum or aluminum oxide, in the following molar ratio of the components: methylate alkali metal/halide or hydride of copper (I) 7 17, modifier/a halide or hydride of copper (I) 0,3 9,7.

8. The method according to p. 7, characterized in that the use of the catalytic system, optionally containing methylate titanium at a molar ratio of methylate group element lanthanum to methylate titanium from 0.3 to 0.8.

9. The method according to p. 7, characterized in that the concentration of copper in solution, obtained from solvent and catalyst system, equal to from 0.01 to 0,09 molar.

10. The method according to p. 7, characterized in that the reaction temperature is in the range of 60 150oC.

11. The method according to p. 7, characterized in that the reaction is carried out at a partial pressure of the reactants in excess of 1 MPa.

12. The method according to p. 11, characterized in that the partial pressure of the reactants from 3 to 7 MPa.

13. The method according to p. 7, characterized in that methanol is added in an amount necessary to polucheniya in number, necessary to obtain a molar ratio HCOORf/Cu from 4 to 400.

15. The method according to p. 7, wherein Rfis1- C10is an alkyl group.

16. The method according to p. 15, wherein Rfis1is an alkyl group.

17. The method according to p. 7, characterized in that reacts with H2when the molar ratio of CO/H2from 0.5 to 5.

18. The method according to p. 17, characterized in that the molar ratio of CO/H2is 1.5 to 3.5.

 

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