EP3962890A1 - Katalysatoren für die katalytische synthese von harnstoff - Google Patents

Katalysatoren für die katalytische synthese von harnstoff

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Publication number
EP3962890A1
EP3962890A1 EP20722301.7A EP20722301A EP3962890A1 EP 3962890 A1 EP3962890 A1 EP 3962890A1 EP 20722301 A EP20722301 A EP 20722301A EP 3962890 A1 EP3962890 A1 EP 3962890A1
Authority
EP
European Patent Office
Prior art keywords
formamide
substituted
urea
ruthenium
use according
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.)
Withdrawn
Application number
EP20722301.7A
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German (de)
English (en)
French (fr)
Inventor
Christoph GLOTZBACH
Nils Tenhumberg
Tarek El Hawary
Yevgeny Makhynya
Walter Leitner
Jürgen Klankermayer
Hannah Schumacher
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.)
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
Original Assignee
ThyssenKrupp AG
ThyssenKrupp Industrial Solutions AG
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Application filed by ThyssenKrupp AG, ThyssenKrupp Industrial Solutions AG filed Critical ThyssenKrupp AG
Publication of EP3962890A1 publication Critical patent/EP3962890A1/de
Withdrawn legal-status Critical Current

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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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • the invention relates to a ruthenium catalyst for the catalytic synthesis of urea.
  • urea is an important building block for organic products, such as Melamine, and a raw material for synthetic resins and fibers. It is used as an additive for cattle feed and in the production of pharmaceuticals and
  • Urea is produced on an industrial scale almost exclusively in a high-pressure synthesis from ammonia (NH 3 ) and carbon dioxide (C0 2 ) at around 150 bar and around 180 ° C. Both input materials usually come from an ammonia plant, which is usually in close proximity to a urea plant.
  • Ammonium hydrogen carbonate and water are produced. This is done in an apparatus called a carbamate condenser.
  • the reaction mixture leaves the carbamate condenser in the direction of the urea reactor, where the actual conversion to urea takes place. Because the carbamate is a highly corrosive medium, it is special at many points in the process
  • Oxidizing agents see e.g., K. Kondo et al., Angew. Chem. 1979, 91, 761-761).
  • these routes require the use of highly toxic reactants and produce stoichiometric amounts of by-products. Therefore, a catalytic route to urea is very desirable.
  • Substituted urea derivatives can be prepared catalytically via various routes, using CO and C0 2 or other carbonylating agents.
  • the synthesis of substituted urea derivatives by means of CO is described, for example, in DJ Diaz et al., Eur. J. Org. Chem. 2007, 2007, 4453-4465.
  • the synthesis of substituted urea derivatives by means of CO 2 is described, for example, in P. Munshi, et al., Tetrahedron Lett. 2003, 44, 2725-2727.
  • Synthesis with other carbonylating agents is described, for example, in A. Basha, Tetrahedron Lett.
  • Ammonia is the common starting material in the synthesis of urea. Furthermore, C0 2 is a readily available feedstock for urea synthesis. When looking for a catalytic route to the synthesis of urea based on C0 2 , a two-step process using formamide as an intermediate was considered as the starting point, as shown in Scheme 1:
  • the invention is based on the object of providing a catalyst for the catalytic synthesis of urea in order to overcome the disadvantages of the conventional non-catalytic processes described above, in particular for a synthesis based on formamide as the starting material.
  • a suitable catalyst for the synthesis of urea the by-product formation, e.g. of ammonium carbamate, to be reduced or avoided entirely.
  • the reaction should be able to be carried out under the mildest possible pressure and temperature conditions and the catalyst should have high catalytic productivity.
  • the systems that are required for the synthesis with the catalyst should be as simple and inexpensive as possible.
  • Formamide or formamide and ammonia were used as starting materials for the synthesis.
  • the invention relates to the use of a ruthenium-phosphine complex as a catalyst for the catalytic synthesis of urea, the synthesis preferably comprising the reaction of formamide or formamide with ammonia in the presence of the ruthenium-phosphine complex as a catalyst with the formation of urea and hydrogen .
  • the synthesis preferably comprises the reaction of formamide with ammonia in the presence of the ruthenium-phosphine complex as a catalyst with the formation of urea and hydrogen.
  • an alternative synthesis comprises the conversion of formamide in the presence of the ruthenium-phosphine complex as a catalyst with the formation of urea and hydrogen, with this alternative also forming CO becomes.
  • the ruthenium-phosphine complex has one or more phosphine ligands.
  • the phosphine can be a simple phosphine (monophosphine), a compound with two phosphine groups (diphosphine), a compound with three phosphine groups (triphosphine) or a compound with more than three phosphine groups.
  • the phosphines are in particular trivalent
  • the phosphine is in particular a tertiary phosphine or has two, three or more tertiary phosphine groups.
  • the phosphine is, for example, a compound PR J R 2 R 3 , in which R 1 , R 2 and R 3 each independently represent an organic radical.
  • Substituents R 1 , R 2 and R 3 are preferably each, independently of one another, substituted or unsubstituted alkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.
  • Groups alkyl, aryl and heteroaryl are also examples of these groups if they are present as substituents of a group.
  • Alkyl here also includes cycloalkyl.
  • alkyl are linear and branched Ci-C 8 -alkyl, preferably linear and branched Ci-C 6 -alkyl, for example
  • Substituted alkyl can have one or more substituents, e.g.
  • Halide such as chloride or fluoride, aryl, heteroaryl, cycloalkyl, alkoxy, for example CC 6 alkoxy, preferably Ci-Cp alkoxy, or aryloxy.
  • Unsubstituted alkyl is preferred.
  • aryl are selected from homoaromatic compounds with a molecular weight below 300 g / mol, preferably phenyl, biphenyl,
  • heteroaryl examples include pyridinyl, pyrimidinyl, pyrazinyl, triazolyl,
  • Preferred examples are pyridinyl, pyrimidinyl, quinolinyl, pyrazolyl, triazolyl, isoquinolinyl, imidazolyl and oxazolidinyl, the heteroaryl with the
  • Phosphorus group of the phosphine can be linked via any atom in the ring of the selected heteroaryl.
  • Substituted aryl and substituted heteroaryl can have one, two or more substituents.
  • suitable substituents for aryl and heteroaryl are alkyl, preferably Ci-C 4 -alkyl, eg methyl, ethyl, n-propyl, or iso-propyl, perfluoroalkyl, eg -CF 3 , aryl, heteroaryl, cycloalkyl, alkoxy, eg Ci -C 6 -alkoxy, preferably Ci-C 4 -alkoxy, aryloxy, alkenyl, for example C 2 -C 6 -alkenyl, preferably C 3 -C 6 -alkenyl, silyl, amine and fluorene.
  • Unsubstituted aryl, in particular phenyl, and unsubstituted heteroaryl are preferred.
  • the phosphine in the ruthenium-phosphine complex is PR 1 R 2 R 3 , wherein R 1 , R 2 and R 3 are independently substituted or unsubstituted heteroaryl or substituted or
  • unsubstituted aryl in particular phenyl
  • phenyl are, for example tri (heteroaryl) phosphine or tri (aryl) phosphine, or a PR 1 R 2 R 3 , where R 1 is alkyl and R 2 and R 3 are independently substituted or unsubstituted heteroaryl and / or substituted or unsubstituted aryl, especially phenyl, are, for example
  • Di (heteroaryl) alkyl phosphine or di (aryl) alkyl phosphine Di (heteroaryl) alkyl phosphine or di (aryl) alkyl phosphine.
  • the phosphine in the ruthenium-phosphine complex is particularly preferably a compound with two phosphine groups (diphosphine), a compound with three phosphine groups (triphosphine) or a compound with more than three
  • Phosphine groups the phosphine being particularly preferably a triphosphine.
  • the phosphines with two or more phosphine groups are preferably derived from two or more identical or different phosphines PR 1 R 2 R 3 as described above, with at least one substituent of the phosphines one or more other substituents of the phosphines to form a common group, for example a di-, trivalent or higher-valent alkylene group, is linked as a bridge unit.
  • the above information on the substituents and preferred substituents or phosphines apply analogously to the
  • the ruthenium-phosphine complex contains more than one phosphine group, i. that in the coordination sphere of ruthenium as ligands two or more
  • Monophosphine at least one diphosphine or triphosphine or one
  • bonds between the ruthenium and the phosphine group are formed at least temporarily during the reaction, e.g. a covalent or coordinative bond. It should be noted that the bonds between the ruthenium and the phosphine group are formed at least temporarily during the reaction, e.g. a covalent or coordinative bond. It should be noted that the bonds between the ruthenium and the phosphine group are formed at least temporarily during the reaction, e.g. a covalent or coordinative bond.
  • the phosphine can be used in excess, so that unbound phosphines or phosphine groups can also be present in the reaction mixture.
  • Ruthenium-triphosphine complexes are particularly preferred, the bridge unit between the phosphorus atoms in the triphosphine being an alkyl or alkylene unit, while the other ligands on the phosphorus are substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.
  • the ruthenium-triphosphine complex comprises a triphosphine of the general formula I.
  • R 1 to R 6 are independently substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, preferably substituted or unsubstituted aryl, and R 7 is hydrogen or an organic component, preferably alkyl, cycloalkyl or aryl. Examples of suitable
  • aryl and heteroaryl are mentioned above, alkyl, in particular methyl, ethyl, n-propyl, iso-propyl, alkoxy, eg. Methoxy, and perfluoroalkyl, e.g. B. -CF 3 .
  • the substituted or unsubstituted aryl is preferably unsubstituted aryl, in particular phenyl.
  • the substituted or unsubstituted heteroaryl is preferably unsubstituted heteroaryl.
  • R 1 to R 6 can be identical or different, and they are preferably identical.
  • R 1 to R 6 are particularly preferably substituted or unsubstituted phenyl.
  • the substituted aryl, especially substituted phenyl can have one, two or more substituents, e.g. B. in the ortho and / or para position. Examples of suitable substituents are mentioned above, alkyl, in particular methyl, ethyl, n-propyl, iso-propyl, alkoxy, such as methoxy or perfluoroalkyl, such as -CF 3 , are preferred.
  • R 7 is particularly preferably an alkyl, more preferably methyl or ethyl, especially methyl.
  • a particularly preferred phosphine ligand for the ruthenium-phosphine complex is l, l, l-tris (diphenylphosphinomethyl) ethane (triphos), which follows
  • the ruthenium-phosphine complex can contain one or more other ligands (non- Phosphine ligands), such as carbenes, amines, amides, phosphites, phosphoamidites, phosphorus-containing ethers or esters, sulfides, trimethylene methane, cyclopentadienyl, allyl, methylallyl, ethylene, cyclooctadiene, acetylacetonate,
  • ligands non- Phosphine ligands
  • other ligands such as carbenes, amines, amides, phosphites, phosphoamidites, phosphorus-containing ethers or esters, sulfides, trimethylene methane, cyclopentadienyl, allyl, methylallyl, ethylene, cyclooctadiene, acetylacetonate,
  • the one or more further ligands are preferably selected from trimethylene methane, cyclopentadienyl, allyl, methylallyl, ethylene, cyclooctadiene, acetylacetonate, acetate, hydride, halide, phenolate, CO or a combination thereof, with trimethylene methane (tmm) being particularly preferred.
  • trimethylene methane (tmm) trimethylene methane (tmm) being particularly preferred.
  • catalytic reaction sequence can easily be substituted by reactant species. Furthermore, a catalyst precursor can be stabilized with these ligands.
  • the ruthenium-phosphine complex has the following general formula II:
  • A is a triphosphine of general formula I as defined above and L are each independently monodentate ligands, two monodentate ligands L being replaced by one bidentate ligand or three monodentate ligands L by a tridentate ligand can be replaced.
  • Examples of the mono-, bi- or tridentate ligands L are the other ligands mentioned above (non-phosphine ligands), whereby they are preferably selected from trimethylene methane, cyclopentadienyl, allyl, methylallyl, ethylene, cyclooctadiene, acetylacetonate, acetate, hydride, Halide, phenolate, CO or a combination thereof, with trimethylene methane (tmm) being particularly preferred.
  • the ligand tmm is a tridentate ligand.
  • a particularly preferred ruthenium-triphosphine complex has the following structure:
  • substituents R are each independently substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, preferably substituted or unsubstituted aryl
  • L are each independently monodentate ligands, two monodentate ligands L being replaced by a bidentate ligand or three monodentate ligands L. can be replaced by a tridentate ligand.
  • suitable substituents for aryl and heteroaryl are mentioned above, alkyl, in particular methyl, ethyl, n-propyl, iso-propyl, alkoxy, for example methoxy and perfluoroalkyl, such as -CF 3 , are preferred.
  • the substituted or unsubstituted aryl is preferably unsubstituted aryl, in particular phenyl.
  • the substituted or unsubstituted heteroaryl is preferably an unsubstituted heteroaryl.
  • the substituents R can be identical or different, and they are preferably identical.
  • R is particularly preferably substituted or unsubstituted phenyl.
  • the substituted phenyl can have one, two or more substituents, in particular in the ortho and / or para position. Examples of suitable
  • alkyl in particular methyl, ethyl, n-propyl, iso-propyl, alkoxy, for example methoxy, and perfluoroalkyl, such as -CF 3 , are preferred.
  • the triphosphine ligand is particularly preferably triphos.
  • Examples of the mono-, bi- or tridentate ligands L are the other ligands mentioned above (non-phosphine ligands), whereby they are preferably selected from trimethylene methane, cyclopentadienyl, allyl, methylallyl, ethylene, cyclooctadiene, acetylacetonate, acetate, hydride, Halide, phenolate, CO or a combination thereof, with trimethylene methane (tmm) being particularly preferred.
  • a particularly preferred ruthenium-phosphine complex is [Ru (Triphos) (tmm)] with the following structural formula:
  • the ruthenium-phosphine complex can also be prepared in situ in the reaction mixture for the reaction.
  • the in situ production of the ruthenium-phosphine complex is possible from catalyst precursors, the phosphines, especially triphosphines, and, if appropriate, further ligands.
  • the ruthenium-phosphine complex can be more homogeneous in the catalytic conversion of formamide or of formamide with ammonia to urea
  • Catalyst or can be used as an immobilized catalyst. Also,
  • the catalytic reaction with the ruthenium-phosphine complex can be carried out homogeneously or heterogeneously, e.g. with an immobilized catalyst in one
  • the catalytic synthesis of urea in particular the catalytic conversion of formamide or of formamide and ammonia, can be carried out continuously or batch-wise, continuous operation being preferred.
  • the catalytic synthesis or catalytic conversion is preferably carried out in an autoclave or a pressure reactor.
  • An autoclave is suitable for batch operation.
  • a pressure reactor is suitable for continuous operation.
  • the catalytic synthesis of urea, in particular the catalytic conversion of formamide or of formamide and ammonia can optionally also be carried out in the presence of an acid as co-catalyst, which can be, for example, a Brnsted acid or a Lewis acid.
  • the acid can be an organic or inorganic acid. The acid can lead to additional activation of the catalyst or the formamide and improve the yield of the reaction.
  • Organoaluminum compounds e.g. Aluminum triflate
  • Scandium compounds such as scandium, perfluorinated copolymers have at least one sulfo group, such as those available under the trade name National ® NR50, or combinations thereof.
  • Conversion of formamide or the catalytic conversion of formamide and ammonia to urea takes place e.g. at a temperature in the range from 50 to 250 ° C, preferably in the range from 120 to 200 ° C, particularly preferably im
  • Conversion of formamide or of formamide and ammonia to urea takes place, for example, at a pressure (reaction pressure) in the range from ambient pressure to 150 bar, preferably in the range from 2 bar to 60 bar, particularly preferably in the range from 5 to 40 bar.
  • reaction pressure in the range from ambient pressure to 150 bar, preferably in the range from 2 bar to 60 bar, particularly preferably in the range from 5 to 40 bar.
  • the amount of ammonia used in the reaction can be in equivalents (eq.) Based on formamide, for example in the range from 1 to 300 eq., Preferably from 4 eq. to 100 eq., particularly preferably from 29 to 59 eq., are. In a preferred embodiment, the reaction takes place at about 29 to 59 eq.
  • Particularly preferably used solvents are dioxane, in particular 1,4-dioxane, or toluene.
  • the reaction is preferably carried out with a high stoichiometric excess of ammonia. This can improve the yield of urea.
  • the suitable reaction time for the catalytic synthesis of urea in particular the catalytic conversion of formamide or preferably of formamide with ammonia, can depend on the others
  • reaction time is expediently the reaction
  • the catalytic synthesis of urea in particular the catalytic conversion of formamide or of formamide with ammonia, can be carried out in the absence or presence of a solvent, in particular an organic solvent.
  • a solvent in particular an organic solvent.
  • ammonia which may be present in excess in the form of liquid or, preferably, supercritical ammonia can function as solvent.
  • a solvent in particular an organic solvent.
  • One solvent or a mixture of two or more solvents can be used, one solvent being preferably used.
  • the solvent is preferably an organic solvent, especially an aprotic organic solvent.
  • the solvent can be polar or non-polar, with non-polar organic solvents being preferred.
  • the solvent is preferably chosen so that the ruthenium-phosphine complex used can be at least partially dissolved therein.
  • the solvent is preferably selected from the group consisting of cyclic and non-cyclic ethers, substituted and unsubstituted Aromatics, alkanes and halogenated hydrocarbons, such as
  • Trichloromethane, and alcohols the solvent preferably being selected from halogenated hydrocarbons, cyclic ethers and substituted or unsubstituted aromatics, preferably from cyclic ethers and substituted or unsubstituted aromatics.
  • aromatics are benzene or benzene which has one or more aromatic substituents (e.g. phenyl) and / or aliphatic substituents (e.g. Ci-Gr-alkyl).
  • Particularly preferred solvents are dioxane, in particular 1,4-dioxane, toluene, and tetrahydrofuran (THF). But also e.g. Dichloromethane or
  • Trichloromethane can be used with advantage.
  • ionic liquids can optionally also be used as solvents.
  • Ionic liquids are known to the person skilled in the art. These are salts that at low temperatures, e.g. are liquid at temperatures not exceeding 100 ° C.
  • the cation of the ionic liquid is e.g. selected from imidazolium, pyridinium, pyrrolidinium, guanidinium,
  • Alkyl groups can be substituted.
  • the anion of the ionic liquid is e.g. selected from halides, tetrafluoroborates, trifluoroacetates, triflates, hexafluorophosphates, phosphinates, tosylates or organic ions, e.g. Imides or amides.
  • the ruthenium-phosphine complex is preferably at least partially or completely in solution in the solvent.
  • the catalytic synthesis of urea in particular the catalytic conversion of formamide or of formamide with ammonia to form urea, is preferably a homogeneous catalytic reaction.
  • the catalyst and starting materials are in solution, i.e. in the same phase.
  • the homogeneous catalysis can enable milder reaction conditions and, if necessary, higher selectivities and higher turnover numbers (turnover number TON and / or turnover frequency TOF).
  • the concentration of the solvent or solvents is, for example, in a range from 5 to 500 ml, preferably from 10 to 300 ml, more preferably from 50 to 250 ml, per 1 mmol of Ru-phosphine complex.
  • concentration of ruthenium-phosphine complex as catalyst during the reaction can be, for example, in the range from 0.05 mol% to 10 mol%, preferably from 0.25 mol% to 5 mol%, particularly preferably 0.5 mol -% to 2 mol%, based on the molar amount of formamide.
  • the ruthenium-phosphine complexes are usually sensitive to air and moisture during production, they are preferably produced with the extensive exclusion of air and moisture, for which conventional methods such as Schlenk techniques and work in a glove box are used.
  • Reaction apparatus e.g. Glass utensils and reagents used are dried and / or de-aerated as required using conventional methods.
  • the catalytic conversion of formamide or of ammonia and formamide takes place expediently, but not necessarily, in an inert gas atmosphere or with the greatest possible exclusion of oxygen, since this minimizes any oxidation of the catalyst.
  • Nitrogen as an inert gas is suitable, for example.
  • the exclusion of oxygen is particularly useful if the hydrogen released during the reaction is to be returned to the NH 3 system and used there for the urea and / or NH 3 synthesis.
  • the catalyst used in the NH 3 synthesis is sensitive to oxygen, so that the introduction of additional oxygen must be avoided.
  • the hydrogen formed in the reaction according to the invention can be used in different ways, namely energetically or materially in a downstream plant, e.g. in an ammonia synthesis plant, for example an ammonia plant for the ammonia-urea complex, in which these compounds are produced in a network.
  • reaction mixture that is obtained from the catalytic conversion of formamide or of formamide and ammonia described above is processed in order to recover the urea formed and to recycle the remaining starting materials, catalyst and, if appropriate, solvent.
  • preparation steps can be carried out which are customary in the state of the art and in industry, e.g. Gas-liquid separation,
  • the product streams that are obtained in the work-up thus include a gas stream, which predominantly consists of hydrogen and
  • Ammonia consists, and a liquid stream, which urea, catalyst, residues of formamide and optionally solvents.
  • the gas stream can be obtained from the reaction mixture obtained at elevated pressure, which is advantageous for later recycling, since the gases do not have to be recompressed. If the gases are to be used, for example for urea and / or NH 3 synthesis, compressed gas is generally necessary.
  • reaction mixture under pressure is preferably subjected to a gas-liquid separation without the pressure being reduced
  • Reaction mixture is drained. This separation can take place with or without prior cooling of the reaction mixture.
  • the processing generally includes the separation of formed
  • urea Residue to a temperature below 0 ° C and then filtration or centrifugation of the residue to obtain urea as a solid.
  • the urea obtained as a solid is then generally freed from residues of catalyst and formamide by washing with a solvent and then subjected to granulation.
  • granulation is understood to mean any compacting, unless stated otherwise.
  • An advantage of the use according to the invention is that no biuret is formed from urea, i. E. Residues from processing containing traces of urea can be recycled as required.
  • the gases can be separated from the reaction mixture in the usual way.
  • a gas such as nitrogen can optionally be used as a stripping agent. Stripping the reaction mixture with nitrogen allows the gaseous components to be driven off better.
  • ammonia can be separated off, which can be returned to the urea synthesis or used for the formamide synthesis.
  • the remaining nitrogen / hydrogen mixture can be fed back into the ammonia or formamide synthesis as synthesis gas makeup.
  • the liquid reaction residue obtained after the gas separation usually contains urea, catalyst, excess formamide and traces of Ammonia and optionally solvents. Some of the urea contained in the reaction residue precipitates even at room temperature. In order to achieve the most complete possible precipitation, it is advantageous to use the
  • the reaction residue is preferably to a temperature of below 0 ° C, more preferably below
  • the solid is separated from the reaction residue, e.g. by filtration or centrifugation.
  • the separated solid mainly contains urea and traces of solvent, formamide and catalyst.
  • the solid obtained can then be purified by washing with solvent and subjected to granulation in order to obtain the urea as a finished product.
  • any remaining liquid residue is usually combined with the washing solution used to wash the solid.
  • the mixture obtained usually contains solvent, catalyst, residues of formamide and traces of urea.
  • the mixture obtained can simply be fed back into the reaction and combined with the make-up or starting material for the conversion of formamide, preferably ammonia. As stated above, no biuret is formed from urea, so that the mixture containing traces of urea can be recycled as desired.
  • excess solvent from the subsequent washing of the solid with solvent can be separated off from the mixture obtained by distillation and, if the quality is sufficient, returned. After separation, the formamide can be returned to the reaction.
  • the catalyst can optionally be reused in the process. When the catalyst is deactivated, the remaining residue can
  • urea and catalyst may be subjected to a recrystallization beforehand in order to separate urea and catalyst from one another and to subject the catalyst to regeneration.
  • reaction mixture was stirred and heated to 110 ° C. for 2 h
  • reaction temperature and the pressure in the cold state (room temperature) about 8-10 bar.
  • room temperature room temperature
  • the catalyst [Ru (Triphos) (tmm)] (7.8 mg, 0.01 mmol) was weighed into a Schlenk tube under an argon atmosphere and dissolved in 1,4-dioxane (2.0 ml). After the addition of formamide (40 ml, 1.00 mmol), the reaction mixture was transferred into the autoclave with a cannula under argon countercurrent. Liquid NH 3 (between 0.5 g and 1.0 g) was added to the autoclave and the autoclave closed.
  • reaction mixture was stirred and placed in an aluminum cone for the respective reaction time the respective reaction temperature is heated. After cooling to room temperature, the autoclave was carefully ventilated. After removing the solvent under reduced pressure, the obtained reaction solution was passed through and 13 C-NMR spectroscopy using mesitylene as an internal standard and determined the yield of urea in relation to formamide.
  • the solvent, reaction temperature and reaction time were varied as shown in Table 1 below.
  • Table 1 also shows the obtained urea yield.
  • the catalyst loading is the amount of catalyst used in mol% based on the amount of formamide used (in mol).
  • the catalyst Ru (Triphos) (tmm) was made in situ from the catalyst precursor
  • the yield of urea was 51%.
  • substituent R is shown in the following table 2, in the event that not all substituents R on the three phosphorus atoms are the same, the substituents R on a first P atom as R 1 , on a second P atom as R 2 and on a third P atom are designated as R 3 .
  • the Complex of Ex. 17 on two phosphine groups each with two phenyl groups and the third phosphine group has two isopropyl groups.
  • the ruthenium triphosphine complex also has the tridentate ligand trimethylene methane.
  • the pressures given in the table refer to room temperature (approx. 23 ° C). The autoclaves were filled at room temperature and then brought to the reaction temperature and pressure.
  • Example 19 corresponds to example 12
  • the three ligands L are shown in the following table 3, one ligand L being designated as L 1 , a second ligand L as L 2 and a third ligand L as L 3 .
  • the three ligands L are together by the
  • tridentate ligand trimethylene methane (tmm) is formed.
  • the pressures given in the table refer to room temperature (approx. 23 ° C). The Autoclaves were filled at room temperature and then on
  • the catalytic activity as a function of the catalyst concentration was tested for the following reaction conditions: Catalyst: [Ru (Triphos) (tmm)], 1 mmol formamide, 2 mL 1,4-dioxane, 0.6 g NH 3 , 150 ° C, 10 h, the catalyst concentration being varied.
  • Catalyst [Ru (Triphos) (tmm)], 1 mmol formamide, 2 mL 1,4-dioxane, 0.6 g NH 3 , 150 ° C, 10 h, the catalyst concentration being varied.
  • the reaction pressure was about 30 bar at the reaction temperature and the pressure in the cold state was about 8-10 bar.
  • Table 4 are those among these
  • Catalyst [Ru (Triphos) (tmm)], 1 mmol formamide, 2 mL 1,4-dioxane, 4 bar NH 3 at room temperature (approx. 23 ° C), 150 ° C, 20 h, with the
  • Catalyst concentration was varied.
  • Catalyst 1 mol% [Ru (Triphos) (tmm)], 1 mmol formamide, 0.6 g NH 3 , 150 ° C., 10 h, the solvent concentration being varied.
  • the reaction pressure was about 30 bar at the reaction temperature and the pressure in the cold state was about 8-10 bar.
  • the solvent was 1,4-dioxane. Table 6 shows the amount of 1,4-dioxane used under these reaction conditions in ml (V (1,4-dioxane) [mL]) and the yields obtained.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP20722301.7A 2019-04-29 2020-04-27 Katalysatoren für die katalytische synthese von harnstoff Withdrawn EP3962890A1 (de)

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