阅读说明：本技术 将硝基芳族化合物直接羰基化为异氰酸酯的非均相催化剂 (Heterogeneous catalyst for the direct carbonylation of nitroaromatics to isocyanates ) 是由 A·库舍尔 C·利赞达拉 S·A·顺克 S·泰特尔巴赫 J·罗特尔 J·贝克特尔 N·S 于 2018-04-04 设计创作，主要内容包括：一种制备芳族异氰酸酯的方法,其通过在催化剂的存在下使硝基芳族化合物与一氧化碳反应而将硝基芳族化合物直接羰基化进行,其特征在于所述催化剂包含多金属材料,所述多金属材料包含一种或多种通式A<Sub>x</Sub>B<Sub>y</Sub>的二元金属间相,其中：A为一种或多种选自Ni、Ru、Rh、Pd、Ir、Pt和Ag的元素,B为一种或多种选自Sn、Sb、Pb、Zn、Ga、In、Ge和As的元素,x在0.1-10的范围内,y在0.1-10的范围内。(A process for preparing aromatic isocyanates by direct carbonylation of nitroaromatics by reaction with carbon monoxide in the presence of a catalyst, characterized in that the catalyst comprises a multimetallic material comprising one or more compounds of the general formula A x B y Wherein: a is one or more elements selected from Ni, Ru, Rh, Pd, Ir, Pt and Ag, B is one or more elements selected from Sn, Sb, Pb, Zn, Ga, In, Ge and As, x is In the range of 0.1 to 10,y is in the range of 0.1-10.)

1. A process for preparing aromatic isocyanates by direct carbonylation of nitroaromatics by reaction with carbon monoxide in the presence of a catalyst, characterized in that the catalyst comprises a multimetallic material comprising one or more compounds of the general formula A_xB_yWherein:

a is one or more elements selected from Ni, Ru, Rh, Pd, Ir, Pt and Ag,

b is one or more elements selected from Sn, Sb, Pb, Zn, Ga, In, Ge and As,

x is in the range of 0.1 to 10,

y is in the range of 0.1-10.

2. The method of claim 1, wherein the step of removing the metal oxide layer comprises removing the metal oxide layer from the metal oxide layer

A is one or more elements selected from Ni, Rh, Pd, Ir and Pt, and

b is one or more elements selected from Sn, Sb, Pb, Ga and In.

3. The method of claim 2, wherein the step of removing the substrate comprises removing the substrate from the substrate

A is Rh, and the component A is,

b is one or more elements selected from Pb, Sn and Sb.

4.A method according to any one of claims 1 to 3, characterised in that the multimetallic material comprises one or more components C, wherein component C comprises a or B or component C consists of a or B, wherein a or B is not an intermetallic phase a_xB_yA part of (a).

5. Method according to any one of claims 1 to 4, characterized in that the multimetallic material comprises one or more component C, wherein component C comprises or consists of one or more elements selected from the group consisting of O, N, C, H, Mg, Ca, Mu, Fe, Co, Ni, Zu, Ga.

6. A method according to any one of claims 1 to 5, characterized in that a multimetallic material is deposited on the support material.

7. The process according to any one of claims 1 to 6, characterized in that the nitroaromatic compound is selected from the group consisting of nitrobenzene, dinitrobenzene, nitrotoluene, dinitrotoluene, trinitrotoluene, nitronaphthalene, nitroanthracene, nitrobiphenyl, bis (nitrophenyl) methane and other mono-and polyaromatic compounds having one or more nitro groups.

8. Process according to any one of claims 1 to 7, characterized in that it is carried out discontinuously.

9. The process according to any one of claims 1 to 7, characterized in that it is carried out continuously.

10. Catalyst for the direct carbonylation of nitroaromatics to the corresponding aromatic isocyanates, comprising a multimetallic material comprising one or more compounds of the general formula A_xB_yWherein:

a is one or more elements selected from Ni, Ru, Rh, Pd, Ir, Pt and Ag,

b is one or more elements selected from Sn, Sb, Pb, Zn, Ga, In, Ge and As,

x is in the range of 0.1 to 10,

y is in the range of 0.1-10.

11. The catalyst according to claim 10, characterized in that

A is one or more elements selected from Ni, Rh, Pd, Ir and Pt, and

b is one or more elements selected from Sn, Sb, Pb, Ga and In.

12. The catalyst according to claim 11, characterized in that

A is Rh, and the component A is,

b is one or more elements selected from Pb, Sn and Sb.

13. Catalyst according to any of claims 10 to 12, characterized in that the multimetallic material comprises one or more components C, wherein component C comprises a or B or component C consists of a or B, wherein a or B is not an intermetallic compound a_xB_yA part of (a).

14. Catalyst according to any of claims 10 to 13, characterized in that the multimetallic material comprises one or more component C, wherein component C comprises or consists of one or more elements selected from O, N, C, H, Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.

15. Catalyst according to any of claims 10 to 14, characterized in that the multimetallic material comprises one or more binary intermetallic crystalline phases selected from the group consisting of: RhpB, Rh4Pb, Rh2, RhSn, Rh2, RhSb, RhGa, Rh10Ga, Rh3Ga, Rh2Ga, Rh4Ga, Rh3Ga, RhGa, RhIn, Rh5Ge, Rh2, RhGe, Rh17Ge, RhGe, IrPb, IrSn, Ir5Sn, IrSn, Ir3Sn, IrSn, Ir5Sn, IrSn, Ir3Sn, IrSn, Ir3, IrSn, Pd13Pb, Pd5Pb, PdSn, Pd3, Pd20Sn, Pd2, PdSn, Pd20Sb, Pd5Sb, Pd8Sb, Pd2, PdSb, PdGa, PdPd 5Ga, Pd7Ga, Pd2, Ru3, Ni3Sn, NiSb, Ni3, Ni.

16. Catalyst according to claim 15, characterized in that the multimetallic material comprises one or more binary intermetallic crystalline phases selected from the group consisting of RhPb, RhPb2, RhSb, Rh2Sb, RhSb2 and Rh2 Sn.

17. The catalyst of any one of claims 10 to 116, characterized in that a multimetallic material is deposited onto the support material.

18. A process for preparing a catalyst as defined in claim 17, comprising steps (i) to (iv):

(i) providing one or more precursors of elements a and B and optionally component C, preferably in the form of a solution;

(ii) depositing a metal precursor on a support material;

(iii) carrying out reduction treatment on the composite material;

(iv) and carrying out heat treatment on the composite material.

19. The method of claim 18, wherein the solution comprises one or more solvents selected from the group consisting of water, alcohols, polyols, acids, and bases.

20. The method according to claim 18 or 19, comprising the steps of:

(iii) contacting a support material comprising a metal precursor with one or more reducing agents in solid, liquid or gaseous form selected from the group consisting of alcohols, hydrocarbons, amines, polyols, Zn powder, H₂、CO、CH₄And C₂H₄And are and

(iv) the support material comprising the metal precursor is reduced by thermal reduction under chemically inert conditions.

21. The method according to any one of claims 18 to 20, wherein steps (iii) and (iv) are performed in one step.

Description of the preferred embodiments

The present invention is further illustrated by the following embodiments and combinations of the embodiments described below.

In general, the invention provides a composition comprising one or more compounds of formula A_xB_yCatalytic direct carbonylation of nitroaromatics to aromatic isocyanates, in which:

a is one or more elements selected from Ni, Ru, Rh, Pd, Ir, Pt and Ag;

b is one or more elements selected from Sn, Sb, Pb, Zn, Ga, In, Ge and As;

A_xB_yx in (b) is 0.1-10, preferably 0.2 to 5, and more preferably 0.5 to 2;

A_xB_yy in (b) is 0.1 to 10, preferably 0.2 to 5, and more preferably 0.5 to 2.

Preferred catalysts comprise one or more compounds of the formula A_xB_yA binary intermetallic phase of wherein

A is one or more elements selected from Ni, Rh, Pd, Ir and Pt;

b is one or more elements selected from Sn, Sb, Pb, Ga and In.

More preferred catalysts comprise one or more compounds of formula A_xB_yA binary intermetallic phase of wherein

A is Rh;

b is one or more elements selected from Pb, Sn and Sb.

Preferably, the multimetallic material consists of at least 85% by weight, more preferably at least 90% by weight and even more preferably at least 95% by weight of one or more intermetallic phases a_xB_yAnd (4) forming.

In one embodiment, the multimetallic material comprises one or more components C, wherein component C consists of or comprises A and/or B, wherein A and/or B is not an intermetallic compound A_xB_yA part of (a). In another embodiment, the multimetallic material comprises one or more components C, wherein component C comprises oneOne or more elements selected from or consisting of one or more elements selected from: o, N, C, H, Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba, Ti, Mn, Fe, Co, Ni, Zn, Ga, preferably comprising or consisting of one or more elements selected from: o, N, C, H, Mg, Ca, Mn, Fe, Co, Ni, Zn and Ga.

Preferably, the multimetallic material is deposited on a support material, typically a crystalline or amorphous support material. In a first preferred embodiment, the support material comprises carbon, graphite, graphene or an intercalation compound. In a second preferred embodiment, the support material comprises a carbide, nitride, boride, silicide, phosphide, antimonide, arsenide, sulfide, selenide or telluride. In a third preferred embodiment, the support material comprises one or more binary and multicomponent oxides, such as MgO, CaO, ZnO, CeO₂、SiO₂、Al₂O₃、TiO₂、ZrO₂、Mn₂O₃、Fe₂O₃、Fe₃O₄、MgAl₂O₄、LaAlO₃、CaTiO₃、CeZrO₄、H₂Al₁₄Ca₁₂O₃₄And other binary and multiple oxides and their respective variants known to those skilled in the art. In a fourth preferred embodiment, the support material comprises, preferably consists of, one or more zeolitic materials, wherein the zeolitic material preferably has a framework structure of the ZSM, MFI, MOR, BEA or FAU type.

The support material may be provided in a form including a powder, dispersion, colloid, particle, shaped body (such as a ring, sphere, extrudate or pellet).

The multimetallic material preferably comprises one or more intermetallic crystalline phases selected from the group consisting of: RhpB, RhpB₂、Rh₄Pb₅、Rh₂Sn、RhSn、RhSn₂、RhSn₄、Rh₂Sb、RhSb、RhSb₂、RhSb₃、RhGa、Rh₁₀Ga₁₇、Rh₃Ga₅、Rh₂Ga₉、Rh₄Ga₂₁、Rh₃Ga₁₆、RhGa₃、RhIn、RhIn₃、Rh₅Ge₃、Rh₂Ge、RhGe、Rh₁₇Ge₂₂、RhGe₄、IrPb、IrSn、Ir₅Sn₇、IrSn₂、Ir₃Sn₇、IrSn₄、IrSn、Ir₅Sn₇、IrSn₂、Ir₃Sn₇、IrSn₄、Pd₃Pb、Pd₁₃Pb₉、Pd₅Pb₃、PdPb、Pd₃Sn、Pd₂₀Sn₁₃、Pd₂Sn、PdSn、Pd₅Sn₇、PdSn₂、PdSn₃、PdSn₄、Pd₃Sb、Pd₂₀Sb₇、Pd₅Sb₂、Pd₈Sb₃、Pd₂Sb、PdSb、PdSb₂、Pd₂Ga、Pd₅Ga₂、Pd₅Ga₃、PdGa、PdGa₅、Pd₇Ga₃、Ru₂Sn₃、RuSn₂、Ru₃Sn₇、RuSb、RuSb₂、RuSb₃、NiPb、Ni₃Sn₄、Ni₃Sn₂、Ni₃Sn、NiSn、Ni₅Sb₂、Ni₃Sb、NiSb₂And NiSb₃. In particular, the multimetallic material comprises one or more materials selected from RhPb, RhPb₂、RhSb、Rh₂Sb、RhSb₂And Rh₂An intermetallic crystal phase of Sn.

The multimetallic material of any one of the preceding embodiments is obtainable by a process comprising steps (i) to (iv):

(i) providing a metal precursor, preferably in solution;

(ii) depositing a metal precursor on a support material;

(iia) an optional drying step;

(iii) carrying out reduction treatment on the composite material;

(iv) and carrying out heat treatment on the composite material.

In step (i), a mixture is prepared comprising a solvent and one or more of A, B and a source of C, wherein the solvent comprises one or more of water, an alcohol, a polyol, an acid, and a base.

In step (ii), the mixture prepared according to step (i) is contacted with a support material using a method selected from the group consisting of shallow bed impregnation, spray impregnation, incipient wetness impregnation and melt impregnation. For removing the solvent, a method selected from evaporation, heating or freeze-drying is preferably used. Also included are precipitation techniques, wherein the support material is prepared in situ from a metal solution or in a separate step. The technique also includes an optional drying step.

The reduction treatment step and the heat treatment steps (iii) and (iv) preferably comprise

(iii) (iii) contacting the material obtained in step (ii) with one or more reducing agents, wherein the reducing agent may be provided in solid, liquid or gaseous form and comprises an alcohol, a hydrocarbon, an amine, a polyol, zinc powder, H₂、CO、CH₄And C₂H₄；

(iv) (iv) reducing the material obtained in step (iii) by thermal reduction under chemically inert conditions.

The heat treatment comprises heating the prepared material under chemically inert conditions, preferably under inert gas (e.g. nitrogen, argon and helium). Heating can be carried out in muffle furnaces, microwave furnaces, rotary kilns, tube furnaces and fluidized beds.

The multimetallic material and the catalyst comprising the multimetallic material of any of the foregoing embodiments are used for the direct carbonylation of nitroaromatics to isocyanates.

Generally, the process for the synthesis of isocyanates from nitroaromatics and carbon monoxide comprises the steps a) to d):

a) providing a reactant mixture M1 comprising a nitroaromatic compound and at least one additional component D, wherein D comprises a suitable solvent;

b1) providing a reactant mixture M2 comprising reactant mixture M1 and carbon monoxide or a mixture of carbon monoxide and an inert gas G, and/or

b2) Providing a reaction mixture R1 comprising a reactant mixture M1 and a carbonylation catalyst comprising a multimetallic material as detailed above;

c) contacting reactant mixture M2 with a carbonylation catalyst comprising, preferably consisting of, multimetallic material I) as detailed above; and/or

d) Contacting reactant mixture R1 with carbon monoxide or a mixture of carbon monoxide and inert gas G;

e) an isocyanate-containing reaction mixture is obtained.

The concentration of the nitroaromatic compound in the mixture M1 is generally in the range of 0.01 to 60% by weight, more preferably in the range of 0.1 to 50% by weight, and still more preferably in the range of 0.1 to 40% by weight. The concentration of component D in the mixture M1 is generally in the range of 40 to 99% by weight, more preferably in the range of 50 to 99% by weight, and further preferably in the range of 60 to 99% by weight.

Suitable nitroaromatics include monoaromatics or polyaromatics having one or more nitro groups: nitrobenzene, dinitrobenzene, nitrotoluene, dinitrotoluene, trinitrotoluene, nitronaphthalene, nitroanthracene, nitrobiphenyl, bis (nitrophenyl) methane and other mono-and polyaromatic compounds having one or more nitro groups. The nitroaromatic compound may also contain other functional groups. For the purposes of the present invention, functional groups are substituents attached to an aromatic ring. The functional group may comprise one or more heteroatoms selected from H, B, C, N, P, O, S, F, Cl, Br and I. Examples of functional groups are hydroxyl, halogen, pendant aliphatic chains, carbonyl, isocyanate, nitroso, carboxyl and amino groups.

Also included are organic nitro compounds containing one or more nitro groups bonded to aliphatic chains, side chains or rings, such as 1, 6-dinitrohexene or nitrocyclohexene, nitrocyclopentene, nitromethane, nitrooctane, bis- (nitrocyclohexyl) -methane.

In a preferred embodiment, the nitroaromatic compound is provided in one or more aprotic organic solvents selected from chlorobenzene, dichlorobenzene, benzene, toluene, THF, dioctyl ether, chloroform, dichloromethane, n-alkanes, cycloalkanes, 1, 2-diphenylbenzene, 1-phenylnaphthalene, ditoluene, 1, 2-dimethylnaphthalene, diphenylmethane, hexadecylbenzene, tetradecylbenzene, dodecylbenzene or Solvesso 150ND and Solvesso 200 ND. Typically, the one or more aprotic organic solvents have a boiling point of from 50 ℃ to 300 ℃, preferably from 100 ℃ to 275 ℃, more preferably from 125 ℃ to 255 ℃.

In a particular embodiment, the solvent may be an isocyanate corresponding to the respective nitroaromatic compound.

Generally, the preparation of the isocyanates is carried out at a temperature of from 50 ℃ to 250 ℃, preferably from 80 ℃ to 190 ℃, more preferably from 100 ℃ to 170 ℃. Generally, the preparation of the isocyanates is carried out at a total pressure of from 1 to 200 bar, preferably from 10 to 150 bar and more preferably from 15 to 100 bar. The carbon monoxide partial pressure is generally from 1 to 150 bar, preferably from 1 to 120 bar, and more preferably from 1 to 100 bar.

In a first embodiment, the isocyanate is prepared discontinuously in batches, comprising the following steps:

a) providing a reactant mixture M1 comprising a nitroaromatic compound and at least one additional component D, wherein D comprises a suitable solvent;

b) providing a reaction mixture R1 comprising a reactant mixture M1 and a carbonylation catalyst comprising the multimetallic material described above;

c) contacting the reaction mixture R1 with carbon monoxide or a mixture of carbon monoxide and an inert gas G;

d) an isocyanate-containing reaction mixture is obtained.

Typically, the concentration of carbonylation catalyst in reaction mixture R1 is in the range of 0.1 to 10 wt.%, preferably in the range of 0.1 to 7.5 wt.%, more preferably in the range of 0.2 to 5 wt.%. The reaction time is usually 0.5 to 24 hours, preferably 2 to 20 hours, more preferably 4 to 12 hours.

In a second embodiment, the isocyanate is prepared continuously in a process comprising the steps of:

a) providing a reactant mixture M1 comprising a nitroaromatic compound and at least one additional component D, wherein D comprises a suitable solvent;

b) a reactant mixture M2 comprising reactant mixture M1 and carbon monoxide or a mixture of carbon monoxide and an inert gas G is provided to obtain reactant mixture M2.

c) Contacting reactant mixture M2 with a carbonylation catalyst comprising, preferably consisting of, multimetallic material I) as detailed above;

d) an isocyanate-containing reaction mixture is obtained.

Generally, in the reaction mixture M2, the partial pressure of carbon monoxide is in the range from 1 to 150 bar, preferably in the range from 1 to 120 bar, and more preferably in the range from 1 to 100 bar.