Method for producing carbon monoxide

Abstract

The present invention concerns a method of production for carbon monoxide using a derivative of formic acid, in particular an alkyl formate. It also concerns a method chosen from among, the method of production of methanol, the method of production of acetic acid (Monsanto and Cativa methods), the method of hydroformylation of olefins (oxo and aldox method, the method of production of hydrocarbons (Fischer-Tropsch method), or the method of carbonylation of nickel (Mond method), comprising a step of production of carbon monoxide using an alkyl formate of formula (I) by the method according to the invention. It further concerns a “CO pump” or “CO liquid storage” method comprising a step of production of carbon monoxide using an alkyl formate of formula (I) according to the method of the invention.

Claims

1. A method of production of carbon monoxide (CO) wherein an alkyl formate of formula (I)
H—COOR  (I) where R is an alkyl comprising 1 to 12 carbon atoms, is put into contact with a catalyst, said method being characterized in that the catalyst is chosen from among: an alcoholate of formula (II)
R′—O-M  (II) wherein R′ is an alkyl comprising 1 to 6 carbon atoms, an alkenyl comprising 2 to 6 carbon atoms, an alkynyl comprising 2 to 6 carbon atoms, or an aryl comprising 6 to 10 atoms; and M is an alkali metal selected from among Li, Na, K, Cs or Rb; or M is a quaternary ammonium of formula (III) ##STR00008## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 represent, independently one from the other, a hydrogen atom, an alkyl comprising 1 to 6 carbon atoms, an aryl comprising 6 to 10 carbon atoms, said alkyl and aryl being optionally substituted; or a nitrogenous organic base selected from among the alkaline bicyclic guanidinates selected from among the bicyclic guanidinates of sodium or potassium; or an alkaline amide substituted by alkyls comprising 1 to 6 carbon atoms; and in that the putting into contact is carried out in a or in a mixture of at least two polar and aprotic solvents selected from among: ethers selected from among diethylic ether or tetrahydrofurane (THF); nitrogenous solvents selected from among N,N-dimethylformamide (DMF), pyridine, N-methyl-2-pyrrolidone or 1-methyl-2-pyrrolidone (NMP); ketones selected from among acetone or butan-2-one; or dimethylsulphoxide (DMSO), at a temperature less than 35° C.

2. The method according to claim 1, characterized in that the alcoholate of formula (II)
R′—OM  (II) wherein R′ is an alkyl comprising 1 to 6 carbon atoms; and M is an alkali metal selected from among Li, Na, K, or Rb.

3. The method according to claim 1, characterized in that the alcoholate of formula (II) is selected from among CH.sub.3—OLi, CH.sub.3—ONa, CH.sub.3—OK, CH.sub.3—ORb, CH.sub.3CH.sub.2—OK, or tBu-OK.

4. The method according to claim 1, characterized in that the alcoholate of formula (II)
R′—OM  (II) wherein R′ is an alkyl comprising 1 to 6 carbon atoms; and M is a quaternary ammonium of formula (III) ##STR00009## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 represent, independently one from the other, a hydrogen atom, an alkyl comprising 1 to 6 carbon atoms, an aryl comprising 6 to 10 carbon atoms, said alkyl and aryl being optionally substituted by one or more polystyrene radical(s).

5. The method according to claim 1, characterized in that the alcoholate of formula (II) is selected from among CH.sub.3—O.sup.−(C.sub.6H.sub.5CH.sub.2)(CH.sub.3).sub.3N.sup.+, or CH.sub.3—O.sup.−(polystyrene-C.sub.6H.sub.4CH.sub.2)(CH.sub.3).sub.3N.sup.+.

6. The method according to claim 1, using, in addition, at least one additive selected from among crown ethers selected from among 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-18-crown-6, benzo-15-crown-5, or dibenzo-15-crown-5; aza-crowns selected from among 1,4,7, 10-tetraazacyclododecane (cyclen), 1,4,7, 10,13,16-hexaazacyclooctadecane (hexacyclen), or diaza-18-crown-6; crown thioethers selected from among 1,5,9,13-tetrathiacyclohexadecane (16-Ane-S.sub.4), or 1,4,7,10,13,16-hexathiacyclooctadecane (18-Ane-S6); or cryptands selected from among [2,1,1], [2,2,1], [2,2,2], [2,2,2]B, [2,2,3], [2,3,3], [3,3,3].

7. The method according to claim 1, characterized in that the temperature for bringing the alkyl formate of formula (I) into contact with the catalyst is less than or equal to 30° C.

8. The method according to claim 1, characterized in that production of carbon monoxide (CO) using an alkyl formate, takes place in an inert atmosphere under pressure of dinitrogen (N.sub.2), argon or a mixture of these gases.

9. The method according to claim 1, characterized in that the amount of catalyst is from 0.1 to 10 mol %, inclusive, compared to the alkyl formate of formula (I).

10. The method according to claim 1, characterized in that the amount of additive used is from 0.1 to 10 mol %, inclusive, compared to the alkyl formate of formula (I).

11. The method according to claim 1, characterized in that the alkyl formate of formula (I) is obtained from formic acid by esterification of the formic acid with an alcohol of formula ROH wherein R is alkyl comprising 1 to 12 carbon atoms.

12. A method selected from among the method of production of methanol, the method of production of acetic acid (Monsanto method), the method of olefin hydroformylation (oxo and aldox method), the method of production of hydrocarbons (Fischer-Tropsch method), or the method of nickel carbonylation (Mond method), comprising a step of production of carbon monoxide using an alkyl formate of formula (I) by a method according to claim 1.

13. The method according to claim 1, characterized in that the catalyst is a nitrogenous organic base selected from among from among sodium or potassium salts of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (or Hhpp) anion; or lithium, sodium or potassium salts of dimethylamide, diethylamide, or diisopropylamide.

14. The method according to claim 1, characterized in that the temperature for bringing the alkyl formate of formula (I) into contact with the catalyst between 10 and 30° C., inclusive.

15. The method according to claim 1, characterized in that the temperature for bringing the alkyl formate of formula (I) into contact with the catalyst is between 15 and 30° C., inclusive.

16. The method according to claim 1, characterized in that the amount of catalyst is from 2 to 5 mol %, inclusive, compared to the alkyl formate of formula (I).

17. The method according to claim 1, characterized in that the amount of additive used is from 2 to 5 mol %, inclusive, compared to the alkyl formate of formula (I).

Description

(1) Other advantages and characteristics of the present invention will appear on reading the following examples given for illustrative purposes and not limiting and the appended figures.

(2) FIG. 1 represents steps (i) to (iii) leading to the production of carbonyl by the method of the invention.

(3) FIG. 2 represents the “CO pump” or “CO liquid storage” method comprising a step of production of carbon monoxide using an alkyl formate of formula (I) according to the method of the invention.

(4) FIG. 3 represents the reaction enabling the preparation of the methanolates of benzyltrimethylammonium CH.sub.3—O.sup.−(C.sub.6H.sub.5CH.sub.2)(CH.sub.3).sub.3N.sup.+ according to the procedure described in Org. Synth. 1958, 38, 5 DOI: 10.15227/orgsyn.038.0005.

(5) FIG. 4 represents the reaction enabling the preparation of the supported version of the methanolates of benzyltrimethylammonium, in particular CH.sub.3—O.sup.− (C.sub.6H.sub.4CH.sub.2)(CH.sub.3).sub.3N.sup.+ according to the procedure described in Org. Synth. 1958, 38, 5 DOI: 10.15227/orgsyn.038.0005.

EXAMPLES

(6) In the examples, carbon monoxide was characterized by:

(7) .sup.13C NMR: Bruker DPX 200 MHz spectrometer

(8) IR: IRAffinity 15 Shimadzu and gas analysis cell

(9) GC: GC-2010 Plus Gas chromatograph Shimadzu

(10) .sup.1H NMR: Bruker DPX 200 MHz spectrometer.

(11) The reagents, catalysts, additives, solvents used are either commercial or prepared according to the indicated reference:

(12) Water: Water Millipore Milli-Q Gradient

(13) DMSO: Carlo Erba 1 L Pure for synthesis

(14) DCM: Carlo Erba 1 L Pure for synthesis

(15) Methanol: Carlo Erba 1 L Anhydrous for analysis

(16) Methyl formate: Acros organics 500 mL 97% CAS: 107-31-3

(17) Ethyl formate: Merck 100 mL Ref: 800891 CAS: 109-94-4

(18) nButyl formate: Alfa Aesar 50 mL Ref: A13882 CAS: 592-84-7

(19) MeOK: Sigma Aldrich 5G 95% CAS: 865-33-8

(20) MeONa: Sigma Aldrich 100G 95% CAS: 124-41-4

(21) MeOLi: Sigma Aldrich 98% Ref: 344370-25G CAS: 865-34-9

(22) EtOK: Sigma Aldrich 100G CAS: 917-58-8

(23) tBuOK: Sigma Aldrich 100G CAS: 865-47-4

(24) MeORb: Preparation according to the method described by S. I.

(25) Drakin, R. K. Kurmalieva, M. K. Karapet'yants, Teoreticheskaya i Eksperimental'naya Khimiya, 1966, Vol 2, pages 40-44

(26) Khpp: Preparation according to: M. P. Coles, P. B. Hitchcock, Aust. J. Chem., 2013, 66, 1124-1130.

(27) Nahpp: Preparation according to: A. A. Mohamed, A. P. Mayer, H. E. Abdou, M. D. Irwin, L. M. Pérez, J. P. Fackler, Inorg. Chem., 2007, 46, 11165-11172.

(28) Khpp: Preparation according to: M. P. Coles, P. B. Hitchcock, Aust. J. Chem., 2013, 66, 1124-1130.

(29) 12C4 (12-crown-4 or 1,4,7,10-tetraoxacyclododecane): Fluka 5 mL CAS: 294-93-9

(30) 18C6 (18-crown-6 or 1,4,7,10,13,16-hexaoxacyclooctadecane): Sigma Aldrich ≥99% 1 G CAS: 17455-13-9

(31) DMF: Sigma Aldrich 99.8% 1 L CAS: 68-12-2

(32) Benzyltrimethyl ammonium chloride: Sigma Aldrich 99% CAS: 56-37-1

(33) polystyrene-(C.sub.6H.sub.4CH.sub.2)(CH.sub.3).sub.3N.sup.+S.sub.2O.sub.3Na.sup.−: Thiosulfate, polymer-bound reference sigma aldrich 589977

(34) Preparation of an Alkyl Formate of Formula (I)

(35) The preparation of alkyl formate by distillation can be carried out according to the following experimental protocol: 1. In air, in a distillation flask introduce pure formic acid as well as water or DMSO (according to the method for obtaining formic acid), or formic acid recovered with its reaction medium by the above-mentioned methods. 2. Add alcohol (2 to 6 molar equivalents in respect to the formic acid, preferably, 3 molar equivalents). 3. Top this with a distillation device (preferably with a Vigreux column) equipped with an outlet trap at a low temperature (from 0° C. to −30° C., preferably −20° C.). 4. The flask is then heated to a temperature chosen according to the formate to enable continuous distillation specific to the formate. 5. The reaction is ended when there is no more alkyl formate condensing.

(36) The table below presents some of the results obtained in the case of methyl formate:

(37) TABLE-US-00001 MeOH Formic (13.8 mL, 318 Yield in isolated acid mmol) Solvent methyl formate (%) 4 mL,  13.8 mL, Water  86% 106 mmol 318 mmol Impurity: 9% MeOH 4 mL,  13.8 mL, DMSO  71% 106 mmol 318 mmol Impurity: 13% MeOH

(38) In this table, the calculated yield is the ratio of the number of moles of methyl formate recovered compared to the number of moles of formic acid introduced corrected by the purity observed by .sup.1H NMR analysis.

(39) Method of Production of Carbon Monoxide (CO) Making Use of an Alkyl Formate of Formula (I) According to the Invention in Closed System

(40) 1. Under inert atmosphere, in glove box, the catalyst, alkyl formate, solvent, and optionally an additive are introduced in a Schlenk tube which is then sealed by a J. Young tap. The order of introduction of the reagents requires putting in the catalyst or the formate last.

(41) 2. The Schlenk tube is then agitated at a temperature between 15 and 30° C.

(42) The table below presents some of the results obtained with DMF as solvent:

(43) TABLE-US-00002 Reagent Catalyst (1 mmol) (5 mol %) Conversion (%).sup.a None None No CO detected None MeOK No CO detected H—COOMe None  0% H—COOMe MeOLi/12C4 12% in 3 h at RT H—COOMe MeOLi 54% in 8 h at 30° C. H—COOMe MeONa/18C6 56% in 3 h at RT H—COOMe MeONa 46% in 3 h at 30° C. H—COOMe MeONa (1.5 mol %) 49% in 3 h at 30° C. H—COOMe MeOK 50% in 4 h at RT H—COOMe MeORb 44% in 3 h at RT H—COOMe EtOK 44% in 1 h at RT H—COOMe tBuOK/18C6 60% in 3 h at RT H—COOMe tBuOK 59% in 3 h at 30° C. H—COOMe Khpp 50% in 4 h at RT H—COOMe Nahpp/18C6 49% in 3 h at RT H—COOMe Nahpp 56% in 3 h at 30° C. H—COOEt MeOK 77% in 2 h3 0 min at RT H—COOEt EtOK 51% in 1 h at RT H—COOn—Bu tBuOK/18C6 40% in 3 h at RT H—COOn—Bu tBuOK 60% in 3 h at 30° C. Solvent used: DMF (600 μL). .sup.aThe percentage of conversion is calculated by .sup.1H NMR analysis of the reaction crude, indirectly by integration of the signal of the alcohol formed at the same time as the CO, compared to the alkyl formate introduced. RT: around 19° C. KHpp: the potassium salt of anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a] pyrimidine. NaHpp: the sodium salt of anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a] pyrimidine.

(44) TABLE-US-00003 Reagent Catalyst (1 mmol) (5 mol %) Solvent Conversion (%).sup.a H—COOMe MeOK DMF 50% in 3 h at RT H—COOMe MeOK NMP 50% in 3 h at RT H—COOMe MeOK THF 14% in 3 h at RT H—COOMe MeOK Et.sub.2O 10% in 3 h at RT H—COOMe MeOK DCM  0% in 3 h at RT .sup.aThe percentage of conversion is calculated by .sup.1H NMR analysis of the reaction crude, indirectly by integration of the signal of the alcohol formed at the same time as the CO, compared to the alkyl formate introduced. RT: around 19° C.

(45) Method of Production of Carbon Monoxide (CO) Making Use of Methyl Formate According to the Invention in Open System 1. Under inert atmosphere, with a single inlet of argon or dinitrogen, the catalyst, solvent, optionally an additive are introduced in a reaction flask equipped with a pressure-equalizing dropping funnel. The order of introduction of the reagents is not important. 2. The methyl formate and the solvent are introduced into the dropping funnel. 3. The argon or dinitrogen inlet is closed. 4. The formate is added. 5. The flask is then agitated at ambient temperature (around 19° C.) by recovering the carbon monoxide by a third neck.

(46) The table below presents some of the results obtained with methyl formate, CH.sub.3OK as catalyst and DMF as solvent:

(47) TABLE-US-00004 H—COOMe CH.sub.3OK DMF (ml) Yield (%).sup.a 1 mmol 5 mol % 17.5 74% in 14 min 6 s at 19° C. 1 mmol 5 mol % 20.4 86% in 2 h 20 min at 19° C. 1 mmol 6 mol % 17.5 74% in 11 min 45 s at 19° C. 1 mmol 7 mol % 17.5 74% in 8 min 16 s at 19° C. 1 mmol 8 mol % 17.5 74% in 8 min 4 s at 19° C. 1 mmol 8 mol % 17.5 74% in 8 min 2 s at 19° C. .sup.aThe yield is calculated by the ratio of n = number of moles of CO recovered (proportional to the volume observed assuming the ideal gas law PV = nRT using P = atmospheric pressure 1013.25 hPa, T = laboratory temperature 19° C., R = ideal gas constant, V = volume of CO observed) to the number of moles of methyl formate used.

(48) Method of Preparation of Methanolates of Benzylmethylammonium CH.sub.3—O.sup.− (C.sub.6H.sub.5CH.sub.2)(CH.sub.3).sub.3N.sup.+ and CH.sub.3—O.sup.− Polystyrene-(C.sub.6H.sub.4CH.sub.2)(CH.sub.3).sub.3N.sup.+

(49) These catalysts are prepared according to the procedure described in Org. Synth. 1958, 38, 5 DOI: 10.15227/orgsyn.038.0005.

(50) Method of Production of Carbon Monoxide (CO) Making Use of an Alkyl Formate of Formula (I) According to the Invention in Closed System

(51) 1. Under inert atmosphere, in glove box, the catalyst, alkyl formate, solvent, and optionally an additive are introduced in a Schlenk tube which is then sealed by a J. Young tap. The order of introduction of the reagents requires putting in the catalyst or the formate last.

(52) 2. The Schlenk tube is then agitated at a temperature between 15 and 30° C.

(53) The table below presents some of the results obtained with DMF as solvent:

(54) TABLE-US-00005 Reagent Catalyst (1 mmol) (5 mol %) Conversion (%).sup.a H—COOMe CH.sub.3—O.sup.−(C.sub.6H.sub.5CH.sub.2)(CH.sub.3).sub.3N.sup.+ 58% in 3 h at RT H—COOMe CH.sub.3—O.sup.−PS—(C.sub.6H.sub.4CH.sub.2)(CH.sub.3).sub.3N.sup.+ 37% in 3 h at RT Solvent used: DMF (600 μL). .sup.aThe percentage of conversion is calculated by 1 H NMR analysis of the reaction crude, indirectly by integration of the signal of the alcohol formed at the same time as the CO, compared to the alkyl formate introduced. RT: around 19° C. PS: polystyrene radical