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WO2025168346A1 - Procédé de production de monoxyde de carbone et procédé de production d'un carburant synthétique - Google Patents

Procédé de production de monoxyde de carbone et procédé de production d'un carburant synthétique

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Publication number
WO2025168346A1
WO2025168346A1 PCT/EP2025/051642 EP2025051642W WO2025168346A1 WO 2025168346 A1 WO2025168346 A1 WO 2025168346A1 EP 2025051642 W EP2025051642 W EP 2025051642W WO 2025168346 A1 WO2025168346 A1 WO 2025168346A1
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WO
WIPO (PCT)
Prior art keywords
compound
process according
decarbonylation
prepared
carried out
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/051642
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German (de)
English (en)
Inventor
Günter Schmid
Iman DINDARLOO INALOO
Romano Dorta
Royel HURTADO
Lisha LOU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Friedrich Alexander Universitaet Erlangen Nuernberg In Vertretung Des Freistaates Bayern
Siemens Energy Global GmbH and Co KG
Original Assignee
Friedrich Alexander Universitaet Erlangen Nuernberg In Vertretung Des Freistaates Bayern
Siemens Energy Global GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102024205409.7A external-priority patent/DE102024205409A1/de
Application filed by Friedrich Alexander Universitaet Erlangen Nuernberg In Vertretung Des Freistaates Bayern, Siemens Energy Global GmbH and Co KG filed Critical Friedrich Alexander Universitaet Erlangen Nuernberg In Vertretung Des Freistaates Bayern
Publication of WO2025168346A1 publication Critical patent/WO2025168346A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • B01J2531/12—Sodium

Definitions

  • the invention relates to a process for producing carbon monoxide and a process for producing a synthetic fuel using the carbon monoxide.
  • carbon monoxide and hydrogen are used in the production of renewable synthetic fuels, such as hydrocarbons or methanol.
  • the hydrogen is produced by electrolysis of water.
  • the carbon monoxide can be produced, for example, by a reverse water gas shift reaction (rWGS): CO 2 + H 2 ⁇ --> CO + H 2 O.
  • rWGS reverse water gas shift reaction
  • a temperature of higher than 800 ° C is required and it is necessary to separate off the water in a complex process.
  • the carbon monoxide can be released from an amide, such as formamide.
  • Formamide for example, can be produced by first reacting ammonia with carbon dioxide and water to form a bicarbonate: (1) NH 3 + CO 2 + H 2 O -> [NH 4 + ][HCO 3 -] and then hydrogenating the bicarbonate to a formate: (2) [NH 4 + ][HCO 3 -] + H 2 -> [NH 4 + ][HCO 2 -] + H 2 O.
  • the formate can dehydrate to form the formamide: (3) [NH 4 + ][HCO 2 -] -> HCONH 2 + H 2 O.
  • Carbon monoxide can be released from the formamide: (4) HCONH 2 -> NH 3 + CO, with the ammonia being reformed in the process.
  • Reactions (1) to (4) together represent the reverse water gas shift reaction CO 2 + H 2 -> CO + H 2 O.
  • 2023PF12464 Foreign Version 2 Another alternative to the water gas shift reaction is the first step of producing formic acid from carbon dioxide and hydrogen: (5) CO 2 + H 2 -> HCOOH.
  • the reaction of ammonia with formic acid leads to the formation of formamide: (6) HCOOH + NH 3 -> HCONH 2 + H 2 O, whereby carbon monoxide is also released here according to (4).
  • reaction (4) A disadvantage of reaction (4) is that hydrogen cyanide and polymers are formed as undesirable by-products. Over acidic catalysts, formic acid can also be decomposed directly by the reaction HCOOH -> CO + H 2 O.
  • the object of the invention is therefore to create a process which enables the release of carbon monoxide with a high yield.
  • the process according to the invention for producing carbon monoxide is carried out by decarbonylation of a compound A, B or C, wherein compound A has the structural formula: OH , the B has the structural formula: has: 2023PF12464 Foreign version 3 5' , where R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ' and R 4 ' are independently H, D, F, an alkyl radical or an aryl radical, where X is an aliphatic bridge, an aromatic bridge, has an ether group, has an ester group, has an amide group or has a urethane group, where n is in a range from 1 to 100,000.
  • the decarbonylation takes place in high yield.
  • the compounds A, B and C thus act as a storage medium for carbon monoxide.
  • X has the alkyl radical or the aryl radical
  • the solubility of the compound C in non-polar solvents can be increased.
  • X has the ether group, the ester group, the amide group or the urethane group
  • the solubility of the compound C in polar solvents can be increased.
  • the decarbonylation takes place analogously to reaction (4) to form an amine.
  • n 1.
  • n can be in a range from 1 to 100 or 1 to 20 or greater than 100.
  • the larger n the greater the ratio of the number of atoms of the amide groups to the number of atoms of the remaining atoms in the compounds A, B or C.
  • the alkyl radical for R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ' and R 4 ' is preferably unbranched or branched.
  • the unbranched alkyl radical preferably has from 1 to 5 carbon atoms.
  • the unbranched alkyl radical can be methyl, ethyl, 2023PF12464 Foreign Version 4 or n-propyl.
  • the branched alkyl radical preferably has from 1 to 10 carbon atoms.
  • the branched alkyl radical can be i-propyl or t-butyl.
  • the aryl radical for R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ' and R 4 ' is preferably substituted, in particular with F, alkyl radicals and/or aryl radicals, or unsubstituted.
  • the aryl radical can be a substituted or unsubstituted phenyl ring.
  • the aryl radical can be pt-butylphenyl.
  • the aliphatic bridge preferably has between 1 and 20 carbon atoms.
  • the aliphatic bridge can be branched or unbranched.
  • the aliphatic bridge can be saturated or unsaturated.
  • the aromatic bridge preferably has between 1 and 30 carbon atoms.
  • the aromatics contained in the aromatic bridge can be substituted, in particular with F, alkyl radicals and/or aryl radicals, or unsubstituted.
  • the aromatic bridge can be partially or fully unsaturated.
  • the aromatic bridge can, for example, have a substituted or unsubstituted phenyl ring.
  • X preferably has the empirical formula (CH 2 ) a O b , where a is in a range from 0 to 20 and b is in a range from 1 to a+1. Peroxide groups are preferably excluded in the ether group.
  • X preferably has the following structural formula: O ( CH 2 ) b , where a+b is in a. 2023PF12464 Foreign version 5
  • X preferably has the following structural formula: O ( CH 2 ) b , where a+b is in one.
  • X has the following structural formula: O ( CH 2 ) a (CH 2 ) b , where a+b is in one.
  • R 5 and R 5 ' are independently H, D, F, an alkyl radical or an aryl radical.
  • the alkyl radical for R 5 and R 5 ' is preferably unbranched or branched.
  • the unbranched alkyl radical preferably has from 1 to 5 carbon atoms.
  • the unbranched alkyl radical can be methyl, ethyl or n-propyl.
  • the branched alkyl radical preferably has from 1 to 10 carbon atoms.
  • the branched alkyl radical can be i-propyl or t-butyl.
  • the aryl radical for R 5 and R 5 ' is preferably substituted, in particular with F, alkyl radicals or aryl radicals, or unsubstituted.
  • the aryl radical can be a substituted or unsubstituted phenyl ring.
  • the aryl radical can be pt-butylphenyl.
  • the decarbonylation is preferably carried out without the presence of a catalyst. The decarbonylation can be carried out, for example, with the addition of heat.
  • the decarbonylation can be carried out in the presence of a catalyst K having the structural formula: + M –– NR 7 , where R 6 is an aryl radical, R 7 is H, D, an aryl radical or an alkyl radical, where M + is selected from the group Li + , Na + , K + , Rb + and Cs + , in particular where the K + is complexed by a crown ether. It has been found that with these 2023PF12464 Foreign Version 7 catalysts, a high yield of carbon monoxide can be achieved. K + and Cs + are particularly preferred because particularly high yields can be achieved with these ions.
  • the decarbonylation can also be carried out in the presence of a strong base as catalyst.
  • the strong base can, for example, be a tert-butyl oxide, in particular sodium tert-butyl oxide or potassium tert-butyl oxide, and/or KOH.
  • Another catalyst for the decarbonylation can be ROM, where M is selected from the group: Na, K, Rb and Cs, where R is selected from the group H, D, alkyl, allyl, aryl, benzyl and vinyl. Examples of these are MeONa, MeOK and MeORb.
  • R 2 NM Another catalyst for decarbonylation can be R 2 NM, where M is selected from the group consisting of Na, K, Rb, and Cs, and R is selected from the group consisting of H, D, alkyl, allyl, aryl, benzyl, and vinyl. Examples include Me 2 NK and ME 2 NCs.
  • R 2 NM results in a faster reaction rate than ROM.
  • K + results in better yields and faster reaction rates than Na + .
  • Rb + and Cs + result in better yields and faster reaction rates than K + , although K + has greater industrial applicability than Rb + and Cs + .
  • the amount of catalyst n K compared to the amount of compound A, B or C n A , n B or n C is ⁇ preferably chosen such that a ratio ⁇ is in a ⁇ ⁇ ⁇ ⁇ range from 0.05% to 5%, in particular 0.1% to 2%, a ⁇ ratio ⁇ is in a range from 0.05% to 5%, ⁇ ⁇ ⁇ ⁇ ⁇ in particular 0.1% to 2%, and a ratio ⁇ is in ⁇ ⁇ ⁇ ⁇ a range from 0.05% to 5%, in particular 0.1% to 2%, where n mean is an arithmetic mean of n (ie an arithmetic mean of the chain length of compound A, B or C).
  • the aryl radical for R 6 is preferably a substituted or unsubstituted phenyl ring with the structural formula: R 12 , where R 8 , R 9 , R 10 , R 11 , R 12 are each H, D, F, an alkyl radical or a
  • R 8 , R 9 , R 10 , R 11 and R 12 are independently H or D or particularly preferably, R 8 , R 9 , R 10 and R 11 are independently H or D and R 12 is t-butyl.
  • the aryl radical for R 7 is preferably a substituted or unsubstituted phenyl ring with the structural formula: R 12 ' , where R 8 ', R 9 ', R 10 ' are each H, D, F, an alkyl radical or a Particularly preferably, R 8 ', R 9 ', R 10 ', R 11 ' and R 12 ' are independently H or D or particularly preferably, R 8 ', R 9 ', R 10 ' and R 11 ' are independently H or D and R 12 ' is t-butyl. It is particularly preferred that R 12 and/or R 12 ' is a branched alkyl radical, in particular i-propyl or t-butyl.
  • the catalyst is distributed particularly well in the compound A, B or C when both the catalyst and the compound A, B or C are in a solid state.
  • R 6 and R 7 are identical.
  • the catalyst K is selected from the group: K1: + K - N , 2023PF12464 Foreign version 9 where R 6 and R 7 are identical and R 8 , R 9 , R 10 , R 11 and R 12 are independently H or D, K2: + Cs – N , in which R 6 and R 7 are identical and R 8 , R 9 , R 10 , R 11 and R 12 are independently H or D, K3: + K – N , in which R 6 and R 7 are R 9 , R 10 and R 11 independently R 12 is t-butyl, K4: + Cs – N , where R 6 and R 7 are R 9 , R 10 and R 11 R 12 is independently t-butyl.
  • the compounds K1, K2, K3, and K4 are particularly preferred because the purity of the reaction mass remains very high in the cyclic process involving carbonylation and decarbonylation.
  • the alkyl radical for R 7 is preferably unbranched or branched.
  • the unbranched alkyl radical preferably has 1 to 5 carbon atoms.
  • the unbranched alkyl radical can be methyl, ethyl, or n-propyl.
  • the branched alkyl radical preferably has 1 to 10 carbon atoms.
  • the branched alkyl radical can be i-propyl or t-butyl.
  • R 6 and/or R 7 has the structural formula: 2023PF12464 Foreign version 10 R 12 , where R 12 is H, D, F, or an aryl radical.
  • the crown ether is preferably 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (Kryptofix® 222). It is preferred that the decarbonylation be carried out with the addition of heat. This allows the yields of carbon monoxide to be increased and the reaction time of the decarbonylation to be shortened, or the reaction rate and thus the release rate of carbon monoxide to be controlled. Alternatively, it is preferred that the decarbonylation be carried out without the addition of heat.
  • the solvent can be, for example, tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • N,N-diphenylformamide is synthesized as compound A, which is obtained from triethylammonium formate azeotrope. Furthermore, it is preferred that diphenylamine and triethylammonium formate azeotrope are mixed and the mixture is fractionally distilled under reduced pressure, wherein N,N-diphenylformamide is obtained as compound A in the solid phase.
  • the carbon monoxide is reacted using hydrogen.
  • the synthetic fuel can comprise a hydrocarbon and/or an alcohol, in particular methanol and/or ethanol.
  • exemplary processes for producing the synthetic fuel are Fischer-Tropsch synthesis, involve synthesis gas fermentation and/or involve methanol synthesis according to the following reaction equation CO + 2 H 2 ⁇ CH 3 OH.
  • Preparation of compounds A, B and C It is preferred that compound A is prepared starting from compound D: H and/or wherein the compound E is prepared: 2023PF12464 Foreign version 12 and/or which is produced by the connection F: H 5' .
  • the A is the Compound D of the compounds B forms compound E and decarbonylation of the compounds C forms compound F.
  • Compounds D1, D2, and D3 are commercially available.
  • Polyaniline is also commercially available. Polyaniline can be prepared by oxidative polymerization of aniline. The chain length of the polyaniline can be adjusted, in particular, via the ratio of the amount of an oxidizing agent to the amount of aniline. Derivatives of polyaniline are also accessible via oxidative polymerization.
  • compound A is prepared by reacting compound D with formic acid and/or compound B is prepared by reacting compound E with formic acid and/or compound C is prepared by reacting compound F with formic acid.
  • the formic acid is prepared from a reaction of hydrogen with carbon dioxide.
  • the amide also acts as a hydrogen storage medium.
  • N,N-diphenylformamide (A1) can be prepared by mixing diphenylamine (100 g, 0.591 mol) and formic acid (108 g, 2.35 mol) in a 250 ml round-bottom flask. After stirring for 3 days, a clear solution of A1 is obtained (98% conversion by 1H NMR).
  • N,N-diphenylformamide (A1) formylation is also possible with triethylammonium formate. This eliminates the need to isolate the formic acid.
  • Amines can be used to scrub CO2 , a process known as amine scrubbing. During amine scrubbing, the CO2 is chemically absorbed by the amines in a scrubbing solution. The saturated amines or the solution are then heated to 100–140 degrees Celsius, whereby a large portion of the CO2 is removed. 2023PF12464 Foreign Version 14 becomes gaseous again and is then separated within the separation system.
  • N,N-diphenylformamide (A1) for example, on a 30 g laboratory scale, with recycling of the triethylammonium formate complex 5:2 (azeotrope), is preferably carried out as follows: Diphenylamine (30 g, 0.177 mol) and triethylammonium formate azeotrope (46.7 g, 0.108 mol, corresponding to 0.540 mol of pure FA, formic acid) were placed in a 100 mL round-bottom flask and connected to a fractional distillation apparatus. The mixture was stirred for 2 days at 150 °C under reduced pressure (150-200 mmHg) to obtain a pale yellow solution.
  • a receiver Schlenk tube maintained at -40 °C collected water (low layer) and NEt3 (upper layer) resulting from the reaction.
  • the excess triethylammonium formate azeotrope was recovered as pure reagent by bulb-to-Schlenk distillation at 100 °C (29.3 g, 94% recovery).
  • the white solid remaining in the flask was ground and identified by 1H NMR as diphenylformamide (34.3 g, 97%), which contained only 3% diphenylamine as the sole impurity.
  • N,N-diphenylformamide (A1) N,N-diphenylformamide
  • A1 N,N-diphenylformamide
  • bases such as triethylamine
  • triethylammonium formate is considered as a distillable azeotrope.
  • 2023PF12464 Foreign Version 15 in good yields. The excess azeotrope can be easily recycled at the end of the reaction.
  • compound A is prepared by reacting compound D with carbon dioxide to form a carbonate and/or a bicarbonate, followed by hydrogenation of the carbonate and/or the bicarbonate with hydrogen to form compound A
  • compound B is prepared by reacting compound E with carbon dioxide to form a carbonate and/or a bicarbonate, followed by hydrogenation of the carbonate and/or the bicarbonate with hydrogen to form compound B
  • compound C is prepared by reacting compound F with carbon dioxide to form a carbonate and/or a bicarbonate, followed by hydrogenation of the carbonate and/or the bicarbonate with hydrogen to form compound C.
  • the amide acts as a storage medium for hydrogen.
  • Compound E can be prepared by oxidative polymerization of a monomer M1: NH . Sang-Bum Kim, Ken of Poly(diphenylamine-4,4'-diyl) and Related Random Copolymers by Organometallic Polycondensation. Electrical, Electrochemical, and Optical Properties” in Macromolecules 1998, 31, 988-993.
  • Compound F can be prepared analogously by oxidative polymerization of a monomer M2: 2023PF12464 Foreign version 16 All mentioned of compounds A, B, C, D, E and/or F can be carried out under anhydrous and/or oxygen-free conditions.
  • aromatic systems include furans, thiophenes, pyrroles, oxazoles, thiazoles, imidazoles, isoxazoles, isothiazoles, pyrazoles, pyridines, pyrazines, pyrimidine, 1,3,6-triazines, alpha- or gamma pyrones, benzo[b]furan, benzo[b]thiophene, indoles, 2H-isoindoles, Benzothiazoles, 2-Benzothiophenes, 1H-Benzimidazoles, 1H-Benzotriazoles, 1H-Indazoles, 1,3-Benzoxazoles, 2-Benzofuranes, 7H-Purines, Quinolines, Iso-Quinolines, Quinazolines, Quinoxalines, Phthalazines, 1,2,4-Benzotriazines, Pyrido[2,3-d]pyrimidine, Pyrido[3,2-d]
  • lithium diphenylamide was prepared by adding 1.2 equivalents of n-BuLi (5 mL, 1.12 M) dropwise to a solution of diphenylamine (846 mg, 5.00 mmol) in n-hexane (25 mL). The reaction mixture was stirred until a white 2023PF12464 Foreign Version 17 precipitate formed. After 1.5 hours of stirring, the resulting suspension was filtered through GF/B (Whatman® glass microfiber filter, grade GF/B), washed with n-pentane (3 ⁇ 10 mL), and dried under HV (high vacuum) to obtain 840 mg (96%) of a white solid.
  • GF/B Whatman® glass microfiber filter, grade GF/B
  • the catalysts Na + [NR 6 R 7 -] can be prepared by deprotonating HNR 6 R 7 with sodium hydride.
  • sodium diphenylamide was prepared by dissolving diphenylamine (1692 mg, 10.00 mmol) and sodium hydride (240 mg, 10.0 mmol), each in THF (10 mL). The sodium hydride solution was added dropwise to the diphenylamine solution to form a light yellow solution. After stirring overnight, the reaction mixture was filtered through GF/B, and the solution was dried overnight in HV. The resulting solid was washed with n-pentane (3 ⁇ 5 mL) and dried in HV to obtain a white solid (1797 mg, 94%).
  • the catalysts K + [NR 6 R 7 -] can be prepared by deprotonation of HNR 6 R 7 with benzylpotassium.
  • potassium diphenylamide (K1) was prepared by dissolving benzylpotassium (8.083 g, 62.07 mmol) and diphenylamine (10.51 g, 62.11 mmol), each in THF (50 mL). Both solutions were pre-chilled in the freezer. The orange benzylpotassium solution was added dropwise to the diphenylamine solution to form a yellowish solution. After stirring for 1.5 hours, the reaction mixture was filtered through GF/B, and the yellowish solution was dried overnight in HV.
  • potassium bis(4-(t-butyl)phenyl)amide (K3) was prepared by dissolving benzylpotassium (1.388 g, 10.66 mmol) and bis(4-(t-butyl)phenyl)amine (3.007 g, 10.68 mmol), each in THF (10 mL). Both solutions were pre-chilled in the freezer. The orange benzylpotassium solution was added dropwise to the bis(4-(t-butyl)phenyl)amine solution.
  • Kryptofix® 222 potassium diphenylamide (K@K22 diphenylamide) was prepared by dissolving potassium diphenylamide (186 mg, 0.897 mmol) and Kryptofix® 222 (336 mg, 0.893 mmol) each in THF (3 mL). The Kryptofix® 222 solution was added dropwise to the potassium diphenylamide solution. After stirring for 20 minutes, the reaction mixture was filtered through GF/B, and the resulting solid was dried overnight in HV. The resulting solid was washed with n-pentane (3 ⁇ 3 mL) and dried in HV to yield 279 mg (54%) of a pale yellow solid.
  • Kryptofix® 222 potassium bis(4-(t-butyl)phenyl)amide was prepared by dissolving potassium bis(4-(t-butyl)phenyl)amide (184 mg, 0.575 mmol) and Kryptofix® 222 (217 mg, 0.577 mmol) each in THF (3 mL). The Kryptofix® 222 solution was added dropwise to the potassium bis(4-(t-butyl)phenyl)amide solution to form a yellowish solution. After stirring for 2 hours, the reaction mixture was filtered through GF/B, and the yellowish solution was dried overnight in HV.
  • the catalysts Cs + [NR 6 R 7 -] can be prepared by reducing HNR 6 R 7 with cesium.
  • cesium diphenylamide (K2) was prepared by adding diphenylamine (508 mg, 3.00 mmol) to cesium (412 mg, 3.10 mmol) in 5 mL of THF. The mixture immediately turned dark orange and 2023PF12464 Foreign Version 19 evolved a gas (presumably hydrogen). The reaction mixture was stirred overnight at room temperature. The completion of the reaction was indicated by the cessation of gas evolution.
  • N,N-diphenylformamide (A1) under constant volume: N,N-diphenylformamide (79 mg, 0.4 mmol) was dissolved in THF-D 8 (0.3 mL) and transferred to a Young's NMR tube (total volume of 1 cm 3 ) with a screw-on Teflon cap. Metal N,N-diphenylamide (0.4 mmol) was dissolved in THF (1 mL). From this solution 2023PF12464 Foreign Version 20 10 ⁇ l were taken and added to the N,N-diphenylformamide solution in the Young's NMR tube. The reaction was analyzed hourly for 66 hours at 25 °C by 1 H NMR.
  • Figure 2 in which the conversion c of the amide into the amine and carbon monoxide is plotted against time, shows similar decarbonylation rates as in Figure 1 and an almost quantitative conversion when the catalysts K1 (with both the uncomplexed K + cation and the K + cation complexed with Kryptofix® 222) and K2 are used.
  • diarylamines are efficiently formylated azeotropically at room temperature with formic acid or at 150 °C under reduced pressure with triethylammonium formate. Furthermore, kinetic studies of the catalytic effects of metallic cesium and potassium on the decomposition of diphenylformamide to CO were conducted.

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  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un procédé de production de monoxyde de carbone par décarbonylation d'un composé A, B ou C, le composé A ayant la formule développée suivante : R5-C6(R1-4)-[N(CHO)-C6(R1-4')] n -R5', le composé B ayant la formule développée suivante : R5-[C6(R1-4)-N(CHO)-C6(R1-4')] n -R5', et le composé C ayant la formule développée suivante : R5-[C6(R1-4)-N(CHO)-C6(R1- 4')-X] n -R5', R1, R2, R3, R4, R1', R2', R3' et R4' désignant indépendamment les uns des autres H, D, F, un reste alkyle ou un reste aryle, X étant un pont aliphatique, étant un pont aromatique, comportant un groupe éther, comportant un groupe ester, comportant un groupe amide ou comportant un groupe uréthane, n étant compris entre 1 et 100000. En outre, l'invention concerne un procédé de fabrication d'un carburant synthétique selon lequel le monoxyde de carbone est réduit par utilisation d'hydrogène.
PCT/EP2025/051642 2024-02-08 2025-01-23 Procédé de production de monoxyde de carbone et procédé de production d'un carburant synthétique Pending WO2025168346A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102024201117 2024-02-08
DE102024201117.7 2024-02-08
DE102024205409.7 2024-06-12
DE102024205409.7A DE102024205409A1 (de) 2024-02-08 2024-06-12 Verfahren zum Herstellen von Kohlenmonoxid und Verfahren zum Herstellen eines synthetischen Kraftstoffs

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Title
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