CN113244964B - Metal complex catalyst and diphenyl carbonate synthesis process - Google Patents
Metal complex catalyst and diphenyl carbonate synthesis process Download PDFInfo
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- CN113244964B CN113244964B CN202110620944.9A CN202110620944A CN113244964B CN 113244964 B CN113244964 B CN 113244964B CN 202110620944 A CN202110620944 A CN 202110620944A CN 113244964 B CN113244964 B CN 113244964B
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- 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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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Abstract
The invention discloses a metal complex catalyst and a synthesis process of diphenyl carbonate. The metal complex catalyst comprises: a main active component and a carrier, the main active component being supported on the carrier; the main active component comprises a copper complex and/or a cobalt complex; the copper complex is CuL 2 X 2 The cobalt complex is CoL' X 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein L is N, N-dimethylbenzimidazole (NN-DBDMID), L' is bisiminobiphosphine (PNNP), and X in the copper complex and X in the cobalt complex are each independently an anion. The metal complex catalyst has the advantages of high catalytic activity, high diphenyl carbonate selectivity, low cost, difficult corrosion of a reactor and the like, and the process for synthesizing the diphenyl carbonate by using the catalyst has the advantages of high product yield, simple process, cheap and easily obtained raw materials, no pollution, safety and great reduction of explosion risks.
Description
Technical Field
The invention relates to a metal complex catalyst and a synthesis process of diphenyl carbonate.
Background
Diphenyl carbonate is an important chemical product and can be used as a synthetic raw material of a plurality of important medicines, pesticides and high polymer materials. For example, diphenyl carbonate can be used for the synthesis of engineering plastic polycarbonates and poly-p-hydroxybenzoates, etc.; the method is mainly used for synthesizing methyl isocyanate on pesticides, so as to prepare carbamate pesticide carbofuran; in addition, it is also applicable in the plastics industry, for example in the manufacture of polyarylcarbonates, polyesters of parahydroxybenzoic acid, monoisocyanates and diisocyanates. In addition, diphenyl carbonate can also be used as plasticizers and solvents for nitrocellulose, polyamides, polyesters, and the like.
The preparation process of diphenyl carbonate mainly includes phosgene method, ester exchange method and phenol oxidative carbonylation method. The phosgene method is obtained by reacting phenol and phosgene, and has the defects of long process route and high risk caused by using highly toxic raw material phosgene. The transesterification method is to synthesize diphenyl carbonate by exchanging phenol and dimethyl carbonate, the yield of the route is low, and expensive dimethyl carbonate raw materials are needed to be used, so that the economical efficiency is poor. Phenol oxidative carbonylation is a process for directly synthesizing diphenyl carbonate from phenol, carbon monoxide and oxygen in the presence of a catalyst. The method has the characteristics of simple process, cheap and easily available raw materials, no pollution and the like, but the reaction concentration is easy to reach the explosion limit due to the direct mixing reaction of oxygen and carbon monoxide in a reaction system, so that the explosion risk exists, and the industrialization is not realized.
To solve the aboveThe problem of explosion risk exists in the direct synthesis of diphenyl carbonate by phenol oxidative carbonylation, and an emerging process route for synthesizing diphenyl carbonate by a two-step method is proposed, namely, an active oxygen carrier-phenyl nitrite, phenol, NO and O are introduced in the reaction process 2 The reaction is carried out to generate phenyl nitrite, the phenyl nitrite reacts with CO under low pressure to generate diphenyl carbonate, NO generated in the reaction process returns to the regeneration section to react with raw material phenol, and the generated phenyl nitrite is sent to a main reactor of the reaction section for continuous use after water is removed. The process route avoids potential safety hazards caused by high pressure in an oxygen atmosphere; and the existence of moisture in the whole system is avoided, so that the use of the immobilized heterogeneous catalyst is possible, and the problems of equipment corrosion and the difficulty in separating a catalytic system are avoided. In addition, the starting materials for the process are CO and O 2 The method can be obtained by using the existing water gas production technology and adopting pressure swing adsorption separation, and the raw materials are cheap and easy to obtain. However, industrialization of this emerging green synthesis process depends on the development of efficient, high selectivity catalysts. The prior art has few reports on the process catalyst, and researchers try alumina or silicon dioxide supported noble metal catalysts such as cupric chloride, platinum chloride, palladium chloride and the like, and find that the selectivity of diphenyl carbonate is very low, and the catalysts are expensive and contain chlorine and are easy to corrode.
Disclosure of Invention
The invention aims to solve the technical problems that the catalyst for synthesizing diphenyl carbonate by a two-step method in the prior art has poor selectivity, high cost and easy corrosion due to chlorine, and provides a metal complex catalyst and a synthesis process of diphenyl carbonate. The metal complex catalyst has the advantages of high catalytic activity, high diphenyl carbonate selectivity, low cost, difficult corrosion of a reactor and the like, and the process for synthesizing the diphenyl carbonate by using the catalyst has the advantages of high product yield, simple process, cheap and easily obtained raw materials, no pollution, safety and great reduction of explosion risks.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a metal complex catalystAn agent, comprising: a main active component and a carrier, the main active component being supported on the carrier; the main active component comprises a copper complex and/or a cobalt complex; the copper complex is CuL 2 X 2 The cobalt complex is CoL' X 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein L is N, N-dimethylbenzimidazole (NN-DBDMID), L' is bisiminobiphosphine (PNNP), and X in the copper complex and X in the cobalt complex are each independently an anion.
In the invention, the copper complex CuL 2 X 2 The structural formula of (2) can be as follows:
in the present invention, the cobalt complex CoL' X 2 The structural formula of (2) can be as follows:
in the present invention, the X is preferably I - Or BF 4 - 。
In the present invention, the mass of the metal complex catalyst is 0.2 to 20 parts, preferably 1 to 10 parts, for example 1.2, 2.5, 4 or 7 parts, based on 100 parts of the main active component.
In the present invention, the main active component preferably includes the copper complex and the cobalt complex.
In the invention, the mass of the metal complex catalyst is calculated according to 100 parts, and the main active component comprises 0.5-15 parts of the copper complex and 0.2-5 parts of the cobalt complex; more preferably, the primary active component comprises 0.5 to 5 parts, for example 1, 2, 3 or 4 parts, of the copper complex and 0.2 to 2 parts, for example 0.5, 0.8, 1 or 1.5 parts, of the cobalt complex.
In the present invention, preferably, the metal complex catalyst further comprises a co-active component, the co-active component being supported on the carrier.
Wherein the auxiliary active component comprises iridium complex, and the iridium complex is IrL' 2 X 3 L' is N, N-dimethylnaphthoimidazole (NN-DBNMID), X in the iridium complex, X in the copper complex and X in the cobalt complex are each independently an anion.
Wherein the iridium complex IrL 2 X 3 The structural formula of (2) can be as follows:
wherein the mass of the metal complex catalyst is 0.1 to 5 parts, preferably 0.1 to 2 parts, for example 1 part, based on 100 parts of the co-active component.
Wherein, preferably, the metal complex catalyst comprises the carrier, the copper complex, the cobalt complex and the iridium complex.
Preferably, the mass of the metal complex catalyst is calculated as 100 parts, the copper complex is 0.5-15 parts, the cobalt complex is 0.2-5 parts, and the iridium complex is 0.1-5 parts; more preferably, the copper complex is 0.5 to 5 parts, for example 1 part, 2 parts, 3 parts or 4 parts; the cobalt complex is 0.2 to 2 parts, for example 0.5 parts, 0.8 parts, 1 part or 1.5 parts; the iridium complex is 0.1 to 1 part, for example 0.2 part, 0.5 part or 0.8 part.
In the present invention, the support may be conventional in the art, and may be generally one or more of alumina, ceria, silica gel, activated carbon, pumice, diatomaceous earth, and molecular sieve.
Wherein the molecular sieve may be conventional in the art, preferably one or more of zirconium phosphate molecular sieve, beta molecular sieve and ZSM-11 molecular sieve.
In the present invention, the carrier is preferably one or more of alumina, ceria, zirconium phosphate molecular sieve, beta molecular sieve and ZSM-11 molecular sieve.
The inventor of the invention discovers through a large amount of long-term experimental researches that a copper complex with N, N-dimethyl benzoimidazole as a ligand or a cobalt complex with bisiminodiphosphine as a ligand is used as a main active component, plays a role in steric hindrance shape selection in a molecular catalysis process through the large steric hindrance effect of a ligand organic matter, and improves the selectivity; meanwhile, the space microenvironment of the main component of the metal is regulated, so that electrons and holes of the outer layer of the metal are more prominent, and the reaction is promoted.
The presence of the co-active component in the present invention enhances the steric shape-selective effect described above, increasing the selectivity of the catalyst.
In a preferred embodiment of the present invention, the metal complex catalyst comprises 1 part of the copper complex, 0.2 part of the cobalt complex, 0.1 part of the iridium complex and 98.7 parts of the zirconium phosphate.
In a preferred embodiment of the present invention, the metal complex catalyst comprises 2 parts of the copper complex, 0.5 part of the cobalt complex, 0.2 part of the iridium complex and 97.3 parts of the zirconium phosphate.
In a preferred embodiment of the present invention, the metal complex catalyst comprises 3 parts of the copper complex, 1 part of the cobalt complex, 0.1 part of the iridium complex and 95.9 parts of the beta molecular sieve.
In a preferred embodiment of the present invention, the metal complex catalyst comprises 5 parts of the copper complex, 2 parts of the cobalt complex, 1 part of the iridium complex and 92 parts of the ZSM-11 molecular sieve.
The invention also provides a preparation method of the metal complex catalyst, which comprises the following steps: impregnating the carrier in impregnating solution to obtain a catalyst precursor, and drying the catalyst precursor to obtain the catalyst; the impregnating solution comprises the main active component, alkali and water; the alkali is organic alkali and/or ammonia water, and the pH value of the impregnating solution is not less than 7.
In the present invention, the carrier may be as described above.
In the present invention, the main active component may be as described above.
In the present invention, the organic base may be conventional in the art, preferably an organic amine compound having a boiling point of less than 100 ℃, such as ethylenediamine and/or ethanolamine.
The addition of the base in the present invention can stabilize the structural form of the metal complex.
In the present invention, preferably, the impregnating solution further comprises a co-active component as described above.
In the invention, the impregnating solution can be prepared by adopting a conventional method in the field, and in general, all the components of the impregnating solution are mixed; preferably, the components other than the base are mixed first and then the pH is adjusted to greater than 7 with the base.
Wherein the mixing may be performed using methods conventional in the art.
In the present invention, the impregnation is preferably an isovolumetric impregnation method.
The isovolumetric impregnation method can be performed by a method conventional in the art, generally, the saturated water volume V of the carrier is measured, then an impregnating solution with the volume V is prepared, and the carrier is impregnated into the impregnating solution.
The method for measuring the saturated water volume of the carrier can be conventional in the art, generally, water is dropwise added into the carrier until water absorption reaches saturation, and the added water volume is recorded.
In the present invention, the pH of the impregnation liquid is preferably 7 to 8.
In the present invention, the drying temperature may be conventional in the art, preferably 110 to 120 ℃.
In the present invention, the drying time may be conventional in the art, preferably 3 to 6 hours, more preferably 4 hours.
In the present invention, the preparation method of the metal complex catalyst preferably further comprises pulverizing and molding after the drying.
Wherein the comminution may be carried out by methods conventional in the art, and may generally be milling.
The particle size of the grind may be conventional in the art, preferably 200 mesh.
Wherein the shaping may be carried out by methods conventional in the art, preferably extrusion.
Wherein the shaped form may be conventional in the art, preferably a strip.
The invention also provides a synthesis process of diphenyl carbonate, which comprises the following steps:
phenyl nitrite and CO react under the action of the metal complex catalyst; the temperature of the reaction is 200-300 ℃.
In the present invention, the temperature of the reaction is preferably 220 to 280 ℃, for example 240 ℃, 250 ℃, 260 ℃ or 270 ℃.
In the present invention, the pressure of the reaction may be a conventional pressure for such a reaction, preferably 0.1 to 3MPa, for example 0.5MPa, 1MPa, 1.2MPa, 1.5MPa, 2.5MPa or 2.8MPa.
In the present invention, the molar ratio of the phenyl nitrite to the CO may be conventional in the art, preferably not greater than 1:1, more preferably 1: (1-10), e.g., 1:2, 1:4, 1:5, 1:6, 1:7, 1:8, or 1:9.
In the present invention, the mass space velocity of the reaction may be conventional in the art, preferably 1 to 20 hours -1 。
In the present invention, the feed gas may be fed to the reactor in a manner conventional in the art, preferably by mixing the phenyl nitrite and CO prior to feeding into the catalyst bed of the reactor.
In the present invention, the phenyl nitrite can be prepared by methods conventional in the art, typically phenol, NO and O 2 Reacting to obtain the final product.
Wherein the pressure of the reaction may be conventional in the art, preferably 0.1 to 3MPa.
Wherein the temperature of the reaction may be conventional in the art, preferably 220-300 ℃.
Wherein the reaction is preferably carried out under the action of a catalyst. The catalyst is preferably a copper-based catalyst and/or a cobalt-based catalyst.
In the present invention, the product of the reaction may be isolated by methods conventional in the art, typically by cooling to room temperature. The product is cooled to room temperature, and unreacted CO is still in gas phase and can be recycled; diphenyl carbonate solidifies as a solid and is separated from CO.
In certain preferred embodiments of the present invention, the diphenyl carbonate synthesis process comprises the steps of:
s1: phenol, NO and O 2 Reacting to obtain phenyl nitrite; the temperature of the reaction is 220-300 ℃, and the pressure of the reaction is 0.1-3 MPa;
s2: the phenyl nitrite and the CO react under the action of the metal complex catalyst to obtain the catalyst; the temperature of the reaction can be 200-300 ℃, the pressure of the reaction is 0.1-3 MPa, and the molar ratio of the phenyl nitrite to the CO is 1: (1-10).
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The diphenyl carbonate selectivity of the metal complex catalyst is high and can be higher than or close to 90%, and in the preferred embodiment, 99.1%; the catalyst has high activity, and the conversion rate of phenyl nitrite can be higher than 80 percent;
(2) The metal complex catalyst has low cost, does not contain chlorine and is not easy to corrode the reactor;
(3) The synthesis process of diphenyl carbonate eliminates the hidden danger of explosion caused by direct contact of oxygen and CO, and is an intrinsic and safe reaction process;
(4) The raw materials are cheap and easy to obtain, safe and nontoxic.
(5) The product yield is high, the separation and purification are simple, and the catalyst can be recycled.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The raw materials used in the following examples are all commercially available.
Example 1
S1: measuring saturated water volume of the support
98.7 parts of zirconium phosphate are weighed, water is dropwise added until saturation, and the volume V1 of the added water is recorded.
S2: preparation of metal complex catalysts
1 part of Cu (NN-DBDMID) was weighed out 2 I 2 0.2 part of Co (PNNP) I 2 And 0.1 part of Ir (NN-DBNMID) 2 I 3 Dissolving in water, adjusting pH to 7.5 with ammonia water, and making total volume V1 to obtain soaking solution. 98.7 parts of zirconium phosphate is immersed in the impregnating solution until the impregnating solution is completely absorbed, then dried for 4 hours at the temperature of 110-120 ℃, ground and sieved by a 200-mesh sieve, extruded into strips, and the metal complex catalyst is recorded as YTYC-01.
YTYC-01 comprises 1 part of Cu (NN-DBDMID) 2 I 2 0.2 part of Co (PNNP) I 2 0.1 part of Ir (NN-DBNMID) 2 I 3 And 98.7 parts of zirconium phosphate.
Example 2
S1: measuring saturated water volume of the support
97.3 parts of zirconium phosphate are weighed, water is dropwise added until saturation, and the volume V2 of the added water is recorded.
S2: preparation of metal complex catalysts
Weigh 2 parts Cu (NN-DBDMID) 2 I 2 0.5 part of Co (PNNP) I 2 And 0.2 part of Ir (NN-DBNMID) 2 I 3 Dissolving in water, adjusting pH to 7.5 with ammonia water, and making total volume V2 to obtain soaking solution. 97.3 parts of zirconium phosphate is immersed in the impregnating solution until the impregnating solution is completely absorbed, then dried for 4 hours at the temperature of 110-120 ℃, ground and sieved by a 200-mesh sieve, extruded into strips, and the metal complex catalyst is recorded as YTYC-02.
YTYC-02 includes 2 parts of Cu (NN-DBDMID) 2 I 2 0.5 part of Co (PNNP) I 2 0.2 part of Ir (NN-DBNMID) 2 I 3 And 97.3 parts of zirconium phosphate.
Example 3
S1: measuring saturated water volume of the support
95.9 parts of beta molecular sieve are weighed, water is dropwise added until the beta molecular sieve is saturated, and the volume V3 of the added water is recorded.
S2: preparation of metal complex catalysts
Weigh 3 parts Cu (NN-DBDMID) 2 I 2 1 part Co (PNNP) I 2 And 0.1 part of Ir (NN-DBNMID) 2 I 3 Dissolving in water, adjusting pH to 7.5 with ammonia water, and making total volume V3 to obtain soaking solution. And (3) immersing 97.3 parts of beta molecular sieve in the impregnating solution until the impregnating solution is completely absorbed, drying for 4 hours at 110-120 ℃, grinding, sieving with a 200-mesh sieve, and extruding into strips to obtain the metal complex catalyst which is marked as YTYC-03.
YTYC-03 comprises 3 parts of Cu (NN-DBDMID) 2 I 2 1 part of Co (PNNP) I 2 0.1 part of Ir (NN-DBNMID) 2 I 3 And 95.9 parts of beta molecular sieve.
Example 4
S1: measuring saturated water volume of the support
92 parts of ZSM-11 molecular sieve are weighed, water is dropwise added until the molecular sieve is saturated, and the volume V4 of the added water is recorded.
S2: preparation of metal complex catalysts
Weigh 5 parts Cu (NN-DBDMID) 2 I 2 2 parts of Co (PNNP) I 2 And 1 part Ir (NN-DBNMID) 2 I 3 Dissolving in water, adjusting pH to 7.5 with ammonia water, and making total volume V4 to obtain soaking solution. 92 parts of ZSM-11 molecular sieve is immersed in the impregnating solution until the impregnating solution is completely absorbed, then dried for 4 hours at the temperature of 110-120 ℃, ground and filtered by a 200-mesh sieve, extruded into strips, and the metal complex catalyst is recorded as YTYC-04.
YTYC-04 includes 5 parts of Cu (NN-DBDMID) 2 I 2 2 parts of Co (PNNP) I 2 1 part Ir (NN-DBNMID) 2 I 3 And 92 parts of ZSM-11 molecular sieve.
Comparative example 1
S1: measuring saturated water volume of the support
97.3 parts of beta molecular sieve are weighed, water is dropwise added until the beta molecular sieve is saturated, and the volume V5 of the added water is recorded.
S2: preparation of metal complex catalysts
2 parts of copper acetate and 0.2 part of cobalt complex Co (PNP) I are weighed 2 Wherein PNP is mono-imine diphosphine and 0.5 part of iridium complex Ir (PPY) 2 (PMBP)I 3 Wherein PPY is a first ligand of 2-phenylpyridine, PMBP is a second ligand of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, dissolving in water, regulating pH to 7.5 with ammonia water, and making the total volume V5 to obtain an impregnating solution. And (3) immersing 97.3 parts of beta molecular sieve in the impregnating solution until the impregnating solution is completely absorbed, drying for 4 hours at 110-120 ℃, grinding, sieving with a 200-mesh sieve, and extruding into strips to obtain the metal complex catalyst which is marked as YTYC-05.
YTYC-05 comprises 2 parts of copper acetate, 0.2 part of Co (PNP) I 2 0.5 part of Ir (PPY) 2 (PMBP)I 3 And 97.3 parts of beta molecular sieve.
Comparative example 2
S1: measuring saturated water volume of the support
94.9 parts of alumina are weighed, water is added dropwise until saturated, and the volume V6 of the added water is recorded.
S2: preparation of metal complex catalysts
Weighing 4 parts of copper chloride and 0.8 part of cobalt complex Co (PNP) I 2 Wherein PNP is mono-imine diphosphine and 0.3 part of iridium complex Ir (PPY) 2 (PMBP)I 3 Wherein PPY is a first ligand of 2-phenylpyridine, PMBP is a second ligand of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, dissolving in water, regulating pH to 7.5 with ammonia water, and making the total volume V6 to obtain an impregnating solution. And (3) immersing 94.9 parts of alumina in the immersion liquid until the immersion liquid is completely absorbed, drying for 4 hours at 110-120 ℃, grinding, sieving with a 200-mesh sieve, and extruding into strips to obtain the metal complex catalyst which is marked as YTYC-06.
YTYC-06 comprises 4 parts of copper chloride and 0.8 part of cobalt complex Co (PNP) I 2 0.3 part of Ir (PPY) iridium complex 2 (PMBP)I 3 And 94.9 parts of alumina.
Comparative example 3
S1: measuring saturated water volume of the support
92.7 parts of alumina are weighed, water is added dropwise until saturated, and the volume V7 of the added water is recorded.
S2: preparation of metal complex catalysts
5 parts of copper nitrate and 1.5 parts of cobalt complex Co (PNP) I are weighed 2 Wherein PNP is mono-imine diphosphine and 0.8 part of iridium complex Ir (PPY) 2 (PMBP)I 3 Wherein PPY is a first ligand of 2-phenylpyridine, PMBP is a second ligand of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, dissolving in water, regulating pH to 7.5 by ammonia water, and making the total volume V7 to obtain an impregnating solution. And (3) immersing 92.7 parts of alumina in the immersion liquid until the immersion liquid is completely absorbed, drying for 4 hours at 110-120 ℃, grinding, sieving with a 200-mesh sieve, and extruding into strips to obtain the metal complex catalyst which is marked as YTYC-07.
YTYC-07 contained 5 parts of copper chloride, 1.5 parts of cobalt complex Co (PNP) I 2 0.8 part of Ir (PPY) iridium complex 2 (PMBP)I 3 And 92.7 parts of alumina.
Comparative example 4
S1: measuring saturated water volume of the support
96.3 parts of cerium oxide were weighed, water was dropped dropwise until saturated, and the volume of water added dropwise was recorded as V8.
S2: preparation of metal complex catalysts
1 part of copper acetoxy and 2.0 parts of cobalt complex Co (PNP) I are weighed 2 Wherein PNP is mono-imine diphosphine and 0.7 part of iridium complex Ir (PPY) 2 (PMBP)I 3 Wherein PPY is a first ligand of 2-phenylpyridine, PMBP is a second ligand of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, dissolving in water, regulating pH to 7.5 with ammonia water, and making the total volume V8 to obtain an impregnating solution. 96.3 parts of alumina is immersed in the impregnating solution until the impregnating solution is completely absorbed, then dried for 4 hours at the temperature of 110-120 ℃, ground and sieved by a 200-mesh sieve, extruded into strips, and the metal complex catalyst is recorded as YTYC-08.
YTYC-08 comprises 1 part of copper acetylacetonate, 2.0 parts of cobalt complex Co (PNP) I 2 0.7 part of Ir (PPY) iridium complex 2 (PMBP)I 3 And 96.3 parts of alumina.
Effect examples
The fixed bed reactor is filled with the catalysts obtained in examples 1 to 4 and comparative examples 1 to 4 respectively, the specific reaction temperature, reaction pressure, molar ratio of phenyl nitrite to CO and mass space velocity are set as shown in Table 1, the raw material gas is mixed and then introduced into a fixed bed catalyst bed, the obtained product is subjected to gas-solid separation at room temperature, the obtained gas phase is recycled, and the solid product is diphenyl carbonate.
Table 1 results of catalyst characterization for various examples
As can be seen from Table 1, the catalysts obtained in examples 1 to 4 have high selectivity for synthesizing diphenyl carbonate by catalyzing phenyl nitrite, which is higher than or close to 90%, wherein the catalyst in example 1 has high selectivity even higher than 99%, and the conversion rate of phenyl nitrite is higher than 80%, which indicates that the catalyst has good activity. While the comparative example catalyst has the same metal atom as the example catalyst, the catalytic activity and selectivity are not high.
Claims (22)
1. A metal complex catalyst comprising: a main active component, a co-active component and a carrier, said main active component and said co-active component being supported on said carrier; the main active component comprises a copper complex and a cobalt complex; the copper complex is CuL 2 X 2 The cobalt complex is CoL' X 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein L is N, N-dimethylbenzimidazole and L' is bisiminodiphosphine; the auxiliary active component comprises iridium complex IrL 2 X 3 Wherein L' is N, N-dimethylnaphthoimidazole, X in the copper complex, X in the cobalt complex and X in the iridium complex are each independently I - Or BF 4 - 。
2. The metal complex catalyst according to claim 1, wherein the mass of the metal complex catalyst is 0.2 to 20 parts by mass based on 100 parts by mass of the main active component;
and/or the carrier is one or more of alumina, cerium oxide, silica gel, activated carbon, pumice, diatomite and molecular sieve.
3. The metal complex catalyst according to claim 2, wherein the mass of the metal complex catalyst is 1 to 10 parts by weight based on 100 parts by weight of the main active component;
and/or the molecular sieve is one or more of zirconium phosphate molecular sieve, beta molecular sieve and ZSM-11 molecular sieve.
4. A metal complex catalyst according to claim 3, wherein the mass of the metal complex catalyst is 1.2, 2.5, 4 or 7 parts per 100 parts of the main active component.
5. The metal complex catalyst according to claim 1, wherein the main active component comprises 0.5 to 15 parts by mass of the copper complex and 0.2 to 5 parts by mass of the cobalt complex per 100 parts by mass of the metal complex catalyst;
and/or, the mass of the metal complex catalyst is calculated as 100 parts, and the auxiliary active component is 0.1-5 parts;
and/or the carrier is one or more of alumina, cerium oxide, zirconium phosphate molecular sieve, beta molecular sieve and ZSM-11 molecular sieve.
6. The metal complex catalyst according to claim 5, wherein the main active component comprises 0.5 to 5 parts by mass of the copper complex and 0.2 to 2 parts by mass of the cobalt complex, based on 100 parts by mass of the metal complex catalyst;
and/or the mass of the metal complex catalyst is calculated by 100 parts, and the auxiliary active component is 0.1-2 parts.
7. The metal complex catalyst according to claim 6, wherein the main active component comprises 1 part, 2 parts, 3 parts or 4 parts of the copper complex, and 0.5 part, 0.8 part, 1 part or 1.5 parts of the cobalt complex, based on 100 parts by mass of the metal complex catalyst;
and/or the mass of the metal complex catalyst is calculated as 100 parts, and the auxiliary active component is 1 part.
8. The metal complex catalyst according to claim 5, wherein the mass of the metal complex catalyst is 0.5 to 15 parts by weight of the copper complex, 0.2 to 5 parts by weight of the cobalt complex, and 0.1 to 5 parts by weight of the iridium complex, based on 100 parts by weight of the copper complex.
9. The metal complex catalyst according to claim 8, wherein the mass of the metal complex catalyst is 0.5 to 5 parts by weight of the copper complex, 0.2 to 2 parts by weight of the cobalt complex, and 0.1 to 1 part by weight of the iridium complex, based on 100 parts by weight.
10. The metal complex catalyst according to claim 9, wherein the copper complex is 1 part, 2 parts, 3 parts or 4 parts, the cobalt complex is 0.5 part, 0.8 part, 1 part or 1.5 parts, and the iridium complex is 0.2 part, 0.5 part or 0.8 part based on 100 parts by mass of the metal complex catalyst.
11. The metal complex catalyst of claim 3, wherein the metal complex catalyst comprises 1 part of the copper complex, 0.2 part of the cobalt complex, 0.1 part of the iridium complex, and 98.7 parts of the zirconium phosphate molecular sieve;
alternatively, the metal complex catalyst comprises 2 parts of the copper complex, 0.5 part of the cobalt complex, 0.2 part of the iridium complex and 97.3 parts of the zirconium phosphate molecular sieve;
alternatively, the metal complex catalyst comprises 3 parts of the copper complex, 1 part of the cobalt complex, 0.1 part of the iridium complex and 95.9 parts of the beta molecular sieve;
alternatively, the metal complex catalyst comprises 5 parts of the copper complex, 2 parts of the cobalt complex, 1 part of the iridium complex and 92 parts of the ZSM-11 molecular sieve.
12. A process for preparing a metal complex catalyst as claimed in any one of claims 1 to 11, comprising the steps of: impregnating the carrier in impregnating solution to obtain a catalyst precursor, and drying the catalyst precursor to obtain the catalyst; the impregnating solution comprises the main active component, the auxiliary active component, alkali and water; the alkali is organic alkali and/or ammonia water, and the pH value of the impregnating solution is not less than 7.
13. The method for preparing a metal complex catalyst according to claim 12, wherein,
the organic alkali is an organic amine compound with the boiling point lower than 100 ℃;
and/or the pH of the impregnating solution is 7-8;
and/or the drying temperature is 110-120 ℃;
and/or the drying time is 3-6 h;
and/or, the drying step further comprises crushing and molding.
14. The method for preparing a metal complex catalyst according to claim 13, wherein the organic base is ethylenediamine and/or ethanolamine;
and/or, the drying time is 4h.
15. The method for preparing a metal complex catalyst according to claim 13, wherein the impregnation is performed by an isovolumetric impregnation method;
and/or, the comminuting is grinding;
and/or the molding mode is extrusion;
and/or, the formed shape is strip-shaped.
16. The method for preparing a metal complex catalyst according to claim 15, wherein the isovolumetric impregnation method comprises the steps of: firstly measuring the saturated water volume V of the carrier, preparing impregnating solution with the volume V, and impregnating the carrier in the impregnating solution;
and/or, the particle size of the grinding is 200 mesh.
17. The method for preparing a metal complex catalyst according to claim 16, wherein the method for measuring the saturated water volume of the carrier comprises the steps of: and dropwise adding water into the carrier until the water absorption reaches saturation, wherein the volume of the added water is the saturated water volume of the carrier.
18. A process for synthesizing diphenyl carbonate, which comprises the following steps: reacting phenyl nitrite with CO under the action of the metal complex catalyst according to any one of claims 1 to 11; the temperature of the reaction is 200-300 ℃.
19. The process for synthesizing diphenyl carbonate according to claim 18, wherein the reaction temperature is 220 to 280 ℃;
and/or the pressure of the reaction is 0.1-3 MPa;
and/or the molar ratio of phenyl nitrite to CO is no greater than 1:1;
and/or the mass space velocity of the reaction is 1-20 h -1 ；
And/or, the preparation method of the phenyl nitrite comprises the following steps: phenol, NO and O 2 Reacting to obtain the final product.
20. The process for synthesizing diphenyl carbonate according to claim 19, wherein the reaction temperature is 240 ℃, 250 ℃, 260 ℃ or 270 ℃;
and/or the pressure of the reaction is 0.5MPa, 1MPa, 1.2MPa, 1.5MPa, 2.5MPa or 2.8MPa;
and/or, the molar ratio of phenyl nitrite to CO is 1: (1-10);
and/or the pressure of the reaction in the preparation method of the phenyl nitrite is 0.1-3 MPa; the temperature of the reaction is 220-300 ℃.
21. The process for the synthesis of diphenyl carbonate according to claim 20, wherein the molar ratio of phenyl nitrite to CO is 1:2, 1:4, 1:5, 1:6, 1:7, 1:8 or 1:9.
22. The process for synthesizing diphenyl carbonate according to claim 18, comprising the steps of:
s1: phenol, NO and O 2 Reacting to obtain phenyl nitrite; the temperature of the reaction is 220-300 ℃, and the pressure of the reaction is 0.1-3 MPa;
s2: the phenyl nitrite and CO react under the action of the metal complex catalyst as defined in any one of claims 1 to 11, and the catalyst is obtained; the temperature of the reaction is 200-300 ℃, the pressure of the reaction is 0.1-3 MPa, and the molar ratio of the phenyl nitrite to the CO is 1: (1-10).
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| KR20050119375A (en) * | 2004-06-16 | 2005-12-21 | 실로켐 주식회사 | Oxygen enriching membrane made of metallosiloxane and process preparing the same |
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| CN101856625A (en) * | 2010-06-17 | 2010-10-13 | 南京工业大学 | Non-noble metal homogeneous catalysis system for alcohol oxidative carbonylation and use method thereof |
| CN102553646B (en) * | 2011-12-20 | 2013-10-23 | 厦门大学 | Chiral diamine diphosphine metal compound catalysts as well as preparation method and application thereof |
| EP2650278A1 (en) * | 2012-04-11 | 2013-10-16 | Bayer MaterialScience AG | Method for manufacturing diaryl carbonates from dialkyl carbonates |
| CN103483383A (en) * | 2013-09-11 | 2014-01-01 | 南开大学 | Synthetic method and application of (1E, 2E)-1,2-bi(5-methoxyl-2-diphenylphosphine benzylidene) hydrazine |
| CN104402727B (en) * | 2014-12-04 | 2016-05-11 | 陕西延长石油（集团）有限责任公司 | The method of the continuous diphenyl carbonate synthesis of microreactor |
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