CN113797952B - Catalyst for synthesizing alicyclic amine through selective hydrogenation saturation of benzene ring containing benzene ring amine compounds and preparation method thereof - Google Patents

Catalyst for synthesizing alicyclic amine through selective hydrogenation saturation of benzene ring containing benzene ring amine compounds and preparation method thereof Download PDF

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CN113797952B
CN113797952B CN202010555446.6A CN202010555446A CN113797952B CN 113797952 B CN113797952 B CN 113797952B CN 202010555446 A CN202010555446 A CN 202010555446A CN 113797952 B CN113797952 B CN 113797952B
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benzene ring
ruthenium
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CN113797952A (en
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王利国
杨焕焕
李会泉
徐爽
曹妍
贺鹏
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Institute of Process Engineering of CAS
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
    • C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Abstract

The invention provides a catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring-containing amine compound and a preparation method thereof. The catalyst is used for preparing alicyclic amine by selective hydrogenation saturation of benzene ring of the benzene ring-containing amine compound, does not introduce an alkaline auxiliary agent, and realizes the high-activity and high-selectivity hydrogenation saturation conversion of the benzene ring-containing amine compound into the alicyclic amine under mild conditions.

Description

Catalyst for synthesizing alicyclic amine through selective hydrogenation saturation of benzene ring containing benzene ring amine compounds and preparation method thereof
Technical Field
The invention belongs to the field of catalysts, relates to a catalyst and a preparation method thereof, and particularly relates to a catalyst for synthesizing alicyclic amine by selective hydrogenation saturation of benzene ring-containing amine compounds and a preparation method thereof.
Background
Alicyclic amine is an important organic and fine chemical raw material, and is widely applied to the fields of rubber, food additives, pharmacy, anticorrosion, plastics and the like. The alicyclic diamine is a raw material for synthesizing isocyanate and further synthesizing high-end polyurethane, and a polyurethane product prepared from the alicyclic diamine is not easy to turn yellow and is aging-resistant, so that the alicyclic diamine can be used in high-end fields such as airplanes and high-speed rails. Alicyclic amine is mainly prepared by hydrogenation of corresponding benzene ring amine compounds, but the catalyst activity is poor in the preparation process, so that the reaction time is long and side reactions are more, the target alicyclic amine is poor in selectivity, the burden of subsequent separation is heavy, and the cost is increased.
US20020183556A1 discloses preparation of a catalyst with high-purity alumina carrier loading 4% -8% ruthenium, ruthenium chloride is loaded on the surface of alumina by using a precipitator such as sodium carbonate and sodium hydroxide, then reducing agents such as sodium formate and hydrazine are added, hydrogen is reduced after filtering and drying, the hydrogenation reaction pressure is preferably 10-20 MPa, the PACM mass fraction in the final mixture is 81-89%, the hydrogenation reaction pressure is higher, and the cost is high.
US 9399615B2 reports a Ru-Rh bimetallic catalyst, which is prepared by preparing magnesium aluminum sol, adding an alumina carrier, forming a layer of Mg-Al film on the surface of the carrier, filtering, drying, loading a ruthenium-rhodium precursor, filtering, drying, and calcining, and has a complex preparation method and a poorly controlled process.
CN107362797A discloses a nanometer ruthenium carbon catalyst, which is to treat active carbon with a mixed solution of nitric acid and sodium chlorate for 1-12 hours, and then wash the dried active carbon carrier. And sequentially dropwise adding two ruthenium precursor solutions into the activated carbon suspension for soaking and adsorption, then dropwise adding an alkali solution to adjust the pH value to 8-12, dropwise adding a reducing agent such as sodium borohydride, hydrazine hydrate and the like, filtering, washing and drying to obtain the nano ruthenium carbon catalyst, and carrying out hydrogenation reaction for 4 hours to obtain the MDA conversion rate of 99.9% and the PACM yield of 85.3%. The pretreatment of the activated carbon and the alkali treatment in the dipping process can respectively generate acidic waste liquid and alkaline waste liquid, thereby polluting the environment.
CN 102909035A provides a catalyst of an active carbon-supported active component ruthenium and a cocatalyst component X (Ag, pb, cu, co, ce and the like) for preparing 1, 3-cyclohexyldimethylamine by selective hydrogenation of m-xylylenediamine, the catalyst is prepared by steps of active carbon impregnation with metal, drying, reduction and activation, and evaluation results show that the selectivity of the 1, 3-cyclohexyldimethylamine reaches 91% -98%, but the reaction temperature is higher than 300-500 ℃.
CN 104788323A discloses a catalyst for synthesizing 1, 4-cyclohexyl dimethylamine by hydrogenating p-xylylenediamine, which is prepared by dipping active carbon or silicon dioxide into ruthenium, drying, roasting and reducing. During the reaction, besides the catalyst, raw materials and solvent, alkali metal additives such as LiOH and NaOH are also required to be added, the content of 1, 4-cyclohexyldimethylamine in the mixed solution obtained by filtering after the reaction is finished is 95-99%, although the selectivity of the catalyst is good, an alkaline additive is inevitably required to be added to inhibit the occurrence of side reactions, and the generated alkaline waste liquid has potential environmental risks.
In conclusion, the catalyst system disclosed by the prior patent has the defects of harsh reaction conditions, low activity, poor selectivity, complex preparation process, need of modification by alkaline auxiliaries and the like, so that the development of a novel efficient catalyst for preparing alicyclic amine by selective hydrogenation and saturation of benzene rings of benzene ring amine compounds is of great significance to the production of alicyclic amine.
Disclosure of Invention
In order to solve the technical problems, the application provides a catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring-containing amine compound and a preparation method thereof, the catalyst is used for preparing alicyclic amine by selective hydrogenation and saturation of benzene ring-containing amine compound, no alkaline auxiliary agent is introduced, and high-activity and high-selectivity hydrogenation and saturation conversion of benzene ring-containing amine compound into alicyclic amine is realized under mild conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring amine compounds, which comprises an active component and a carrier, wherein the active component is ruthenium, and the carrier is nitrogen-doped carbon or carbon nitride.
In a preferred embodiment of the present invention, the mass percentage of the active component in the catalyst is 0.1 to 10%, such as 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable, preferably 1 to 8%.
The second purpose of the invention is to provide a preparation method of the catalyst, which comprises the following steps:
(1) Dispersing a carrier in a ruthenium precursor solution, and performing ultrasonic treatment to obtain a suspension;
(2) And (2) adding a reducing agent into the suspension obtained in the step (1) to carry out reduction reaction so as to deposit metallic ruthenium, thereby obtaining the catalyst.
As a preferred embodiment of the present invention, the concentration of the ruthenium precursor solution in step (1) is 0.001 to 0.1g/mL, such as 0.002g/mL, 0.005g/mL, 0.01g/mL, 0.02g/mL, 0.03g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL, 0.07g/mL, 0.08g/mL, or 0.09g/mL, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the ruthenium precursor in step (1) is ruthenium salt.
Preferably, the ruthenium salt comprises any one of ruthenium chloride, ruthenium acetate or ruthenium nitrate, or a combination of at least two of these, typical but non-limiting examples being: a combination of ruthenium chloride and ruthenium acetate, a combination of ruthenium acetate and ruthenium nitrate, a combination of ruthenium nitrate and ruthenium chloride, a combination of ruthenium chloride, ruthenium acetate and ruthenium nitrate, or the like.
Preferably, the ultrasonic treatment in step (1) is carried out for 0.5-24 h, such as 1h, 2h, 5h, 8h, 10h, 12h, 15h, 18h, 20h or 22h, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the suspension in step (1) has a liquid-solid mass ratio of 10 to 40, such as 15.
As a preferable technical scheme of the invention, the carrier is prepared by calcining any one or a combination of at least two of cyanamide, dicyandiamide, melamine, thiourea, urea or guanidine hydrochloride twice.
As a preferable technical scheme, the carrier is prepared by mixing any one or a combination of at least two of cyanamide, dicyandiamide, melamine, thiourea, urea or guanidine hydrochloride and any one or a combination of at least two of chitosan, glucose, sucrose, porous carbon, graphene or graphene oxide and then calcining for two times.
In a preferred embodiment of the present invention, the temperature of the primary calcination is 400 to 700 ℃, for example, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 650 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the time for the first calcination is 0.5 to 5 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours or 4.5 hours, etc., but is not limited to the recited values, and other unrecited values in the range of the values are also applicable.
Preferably, the atmosphere of the primary calcination is air.
Preferably, the temperature of the secondary calcination is 200 to 600 ℃, such as 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or 550 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time of the second calcination is 0.5 to 4 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or 3.5 hours, etc., and is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the atmosphere for the secondary calcination is hydrogen.
According to the invention, the catalyst comprises a porous nitrogen-doped carbon or carbon nitride material and ruthenium loaded on the carrier, the nitrogen-doped carbon or carbon nitride material is prepared by twice calcination, and the second hydrogen atmosphere calcination enables the sheet-shaped stacked structure of the carrier to be thinner, so that the specific surface area and the pore diameter of the nitrogen-doped carbon or carbon nitride carrier are increased, more catalytic active sites and more alkaline active sites are exposed, the performance of the catalyst for activating reactants at a milder temperature and pressure is obviously improved, and the deamination side reaction and the condensation side reaction of a part of the benzene-ring-containing amine compound can be completely inhibited, so that the selectivity on alicyclic amine is higher while the high conversion rate is obtained.
According to the invention, after the catalyst nitrogen-doped carbon or carbon nitride carrier is calcined in a hydrogen atmosphere, the carrier and active metal components have stronger effects, rich N can form effects with Ru, metal particle agglomeration is inhibited, the metal dispersibility is better, and the active sites of metal are more effectively utilized.
As a preferred technical solution of the present invention, the reducing agent in step (2) includes any one of hydrazine hydrate, sodium formate, formaldehyde, sodium borohydride, potassium borohydride, lithium borohydride or lithium aluminum hydride or a combination of at least two of them, and the combination is exemplified by, but not limited to: combinations of hydrazine hydrate and sodium formate, combinations of sodium formate and formaldehyde, combinations of formaldehyde and sodium borohydride, combinations of sodium borohydride and potassium borohydride, combinations of potassium borohydride and lithium borohydride, combinations of lithium borohydride and lithium aluminum hydride or hydrazine hydrate, combinations of sodium formate and sodium borohydride, and the like.
In the present invention, the reduction reaction is preferably performed under ultrasonic conditions.
Preferably, the time for the reduction reaction in step (2) is 0.5 to 24 hours, such as 1 hour, 2 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours or 22 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mass ratio of the reducing agent to the ruthenium precursor in step (2) is 0.5 to 3, such as 1.
In the present invention, the obtained catalyst is preferably washed and dried.
As a preferred embodiment of the present invention, the preparation method of the catalyst comprises the following steps:
(1) Dispersing a carrier in a ruthenium precursor solution with the concentration of 0.001-0.1 g/mL, and performing ultrasonic treatment for 0.5-24 hours to obtain a suspension, wherein the liquid-solid mass ratio of the suspension is (10-40);
the carrier is prepared by calcining any one or the combination of at least two of cyanamide, dicyandiamide, melamine, thiourea, urea or guanidine hydrochloride for two times; or the like, or a combination thereof,
the carrier is prepared by mixing any one or combination of at least two of cyanamide, dicyandiamide, melamine, thiourea, urea or guanidine hydrochloride with any one or combination of at least two of chitosan, glucose, sucrose, porous carbon, graphene or graphene oxide and then calcining for two times;
the temperature of the primary calcination is 400-700 ℃, the time is 0.5-5 h, and the atmosphere is air;
the temperature of the secondary calcination is 200-600 ℃, the time is 0.5-4 h, and the atmosphere is hydrogen;
(2) And (2) adding a reducing agent into the suspension obtained in the step (1) to perform a reduction reaction for 0.5-24 h, so as to deposit metal ruthenium, thereby obtaining the catalyst, wherein the mass ratio of the reducing agent to the ruthenium precursor is 0.5-3.
As the preferable technical scheme of the invention, the catalyst is used for synthesizing alicyclic amine by catalytic hydrogenation saturation of benzene ring-containing amine compounds;
preferably, the benzene ring-containing amine compound comprises at least one benzene ring, at least one amino substituent is connected to the benzene ring, and the general formula of the benzene ring-containing amine compound is shown as formulas I to VI:
Figure BDA0002544057150000061
Figure BDA0002544057150000071
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 And R 9 Are respectively H or C1-C4 alkyl, X is F, cl or Br;
preferably, the benzene ring amine-containing compound comprises any one of 4,4' -diaminodiphenylmethane, m-xylylenediamine, m-phenylenediamine, p-xylylenediamine, p-phenylenediamine, o-xylylenediamine, o-phenylenediamine, p-chloroaniline or aniline;
preferably, the initial reaction pressure for synthesizing alicyclic amine by catalytic hydrogenation saturation of benzene ring of the benzene ring-containing amine compound is 0.5-10 MPa, the reaction temperature is 30-200 ℃, and the reaction time is 0.5-4 h.
The C1-C4 alkyl group may be methyl, ethyl, n-propyl, isopropyl, 1-butyl, 2-butyl, etc., but is not limited to the above groups. The initial reaction pressure may be 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa or 9MPa, the reaction temperature may be 40 ℃, 50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃ or 180 ℃ and the like, the reaction time may be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or 3.5 hours and the like, and the reaction time is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
In the invention, the reaction of synthesizing the lipid by selective hydrogenation and saturation of benzene ring of the benzene ring amine compound can be carried out in solvents such as tetrahydrofuran, methanol, isopropanol, ethanol, cyclohexane, cyclohexylamine or n-butanol, the mass concentration of the raw material MDA is 2-40%, and the dosage of the catalyst is 4-30% of the mass of the raw material.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The invention provides a catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring-containing amine compound, which is used for the reaction, so that the reactant has excellent conversion rate and the reaction has excellent selectivity;
(2) The invention provides a preparation method of a catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring-containing amine compounds, which has simple process and is easy for industrial production.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The implementation provides a preparation method of a catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring-containing amine compounds, which comprises the following steps:
(1) Dispersing 1.74g of carbon nitride carrier in 60mL of ruthenium chloride solution with the concentration of 0.003g/mL, and carrying out ultrasonic treatment for 1 hour to obtain suspension;
the carrier is prepared by twice calcining urea, the temperature of the first calcining is 600 ℃, the time is 4h, and the atmosphere is air; the temperature of the secondary calcination is 220 ℃, the time is 1.5h, and the atmosphere is hydrogen;
(2) And (2) adding 0.21g of sodium borohydride into the suspension obtained in the step (1) to perform a reduction reaction for 2 hours so as to deposit ruthenium metal, and drying to obtain the catalyst.
Evaluation of catalyst Performance: adding 5mmol of 4, 4-diaminodiphenylmethane, 0.24g of the catalyst prepared in the embodiment and 20mL of tetrahydrofuran into a stainless steel autoclave, replacing the autoclave with nitrogen and hydrogen respectively for three times, finally filling 5MPa of H2, heating the autoclave to 130 ℃ after confirming good sealing, and preserving heat for 1.5h; after the reaction was completed, the autoclave was cooled to room temperature with cold water, the gas in the autoclave was released, the autoclave was opened, the catalyst was separated by centrifugation, and the composition of the supernatant liquid was analyzed by gas chromatography, and the results are shown in table 1.
Example 2
The catalyst of example 1 was used in this example, except that the reaction holding time was changed from 1.5 hours to 1 hour in the catalyst performance evaluation process, and the other conditions were exactly the same as in example 1.
Example 3
This example used the catalyst of example 1, except that 4, 4-diaminodiphenylmethane was replaced with p-xylylenediamine and the reaction holding time was replaced from 1.5h to 2.5h in the catalyst performance evaluation, and the other conditions were exactly the same as in example 1.
Example 4
This example used the catalyst of example 1 except that 4, 4-diaminodiphenylmethane was replaced with p-chloroaniline in the evaluation of the catalyst performance, and the other conditions were exactly the same as in example 1
Example 5
This example uses the catalyst of example 1 except that 4, 4-diaminodiphenylmethane was replaced with aniline and the reaction hold time was replaced from 1.5h to 2.5h during the evaluation of the catalyst performance, and the other conditions were exactly the same as in example 1.
Example 6
The catalyst of example 1 was used in this example, except that the target temperature of the reaction vessel was changed from 130 ℃ to 110 ℃ and the reaction holding time was changed from 1.5h to 2h during the evaluation of the catalyst performance, and the other conditions were exactly the same as in example 1.
Example 7
This example used the catalyst of example 1, except that the solvent was replaced from tetrahydrofuran to isopropanol during the evaluation of the catalyst performance, and the other conditions were exactly the same as in example 1.
Example 8
This example used the preparation method of example 1, except that urea in the support preparation process was replaced with dicyandiamide. The performance evaluation conditions of the catalyst obtained in this example were exactly the same as those of example 1.
Example 9
This example employed the preparation method of example 1, except that the carbon nitride of step (1) was replaced with a nitrogen-doped carbon support, while urea in the support preparation process was replaced with a mixture of urea and an appropriate amount of chitosan. In the process of evaluating the performance of the catalyst, the reaction holding time is changed from 1.5h to 2.5h, and other conditions are completely the same as those in example 1.
Example 10
This example used the catalyst of example 1 except that the deionized water in the catalyst preparation step (3) was replaced with tetrahydrofuran, and the conditions for evaluating the performance of the catalyst obtained in this example were exactly the same as those of example 1.
Example 11
The implementation provides a preparation method of a catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring-containing amine compounds, which comprises the following steps:
(1) Dispersing 2g of nitrogen-doped carbon carrier in 40mL of ruthenium chloride solution with the concentration of 0.007g/mL, and performing ultrasonic treatment for 2 hours to obtain a suspension;
the carrier is prepared by twice calcining a mixture of urea and thiourea, wherein the temperature of the once calcining is 550 ℃, the time is 4.5h, and the atmosphere is air; the temperature of the secondary calcination is 500 ℃, the time is 2 hours, and the atmosphere is hydrogen;
(2) And (2) adding 0.26g of lithium borohydride into the suspension obtained in the step (1) to perform reduction reaction for 2 hours to deposit ruthenium metal, and drying to obtain the catalyst.
The catalyst performance evaluation conditions were the same as in example 1.
Example 12
The embodiment provides a preparation method of a catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring of benzene-ring-containing amine compounds, which comprises the following steps:
(1) Dispersing 2g of carbon nitride carrier in 20mL of ruthenium chloride solution with the concentration of 0.015g/mL, and carrying out ultrasonic treatment for 3h to obtain suspension;
the carrier is prepared by twice calcining urea, the temperature of the once calcining is 500 ℃, the time is 5h, and the atmosphere is air; the temperature of the secondary calcination is 550 ℃, the time is 1.5h, and the atmosphere is hydrogen;
(2) And (2) adding 0.30g of potassium borohydride into the suspension obtained in the step (1) to perform reduction reaction for 3 hours to deposit metal ruthenium, and drying to obtain the catalyst.
The catalyst performance evaluation conditions were the same as in example 1.
Comparative example 1
This comparative example employed the production method in example 1, except that carbon nitride in step (1) was replaced with activated carbon.
The catalyst performance evaluation conditions were exactly the same as in example 1.
Comparative example 2
This comparative example employed the production method in example 1, except that carbon nitride in step (1) was replaced with alumina.
The catalyst performance evaluation conditions were exactly the same as in example 1.
Comparative example 3
The comparative example adopts the preparation method in the example 1, and the difference is that in the preparation process of the carrier, urea is calcined only in the primary air atmosphere, secondary calcination is not carried out in the hydrogen atmosphere, in the performance evaluation process of the catalyst, the reaction heat preservation time is replaced from 1.5h to 1h, and other conditions are completely the same as those in the example 1.
TABLE 1
Figure BDA0002544057150000111
Figure BDA0002544057150000121
The applicant states that the present invention is illustrated by the above examples to show the details of the process equipment and process flow of the present invention, but the present invention is not limited to the above details of the process equipment and process flow, which means that the present invention must not be implemented by relying on the above details of the process equipment and process flow. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (16)

1. A catalyst for synthesizing alicyclic amine by selective hydrogenation and saturation of benzene ring-containing amine compounds is characterized by comprising an active component and a carrier, wherein the active component is ruthenium, and the carrier is nitrogen-doped carbon or carbon nitride;
the preparation method of the catalyst comprises the following steps:
(1) Dispersing a carrier in a ruthenium precursor solution, and performing ultrasonic treatment to obtain a suspension;
(2) Adding a reducing agent into the suspension obtained in the step (1) to perform a reduction reaction to deposit ruthenium metal, so as to obtain the catalyst;
the carrier is prepared by calcining any one or the combination of at least two of cyanamide, dicyandiamide, melamine, thiourea, urea or guanidine hydrochloride for two times; or the like, or a combination thereof,
the carrier is prepared by mixing any one or the combination of at least two of cyanamide, dicyandiamide, melamine, thiourea, urea or guanidine hydrochloride with any one or the combination of at least two of chitosan, glucose, sucrose, porous carbon, graphene or graphene oxide and then calcining for two times;
the temperature of the primary calcination is 400-700 ℃, the time is 0.5-5 h, and the atmosphere of the primary calcination is air;
the temperature of the secondary calcination is 200-600 ℃, the time is 0.5-4 h, and the atmosphere of the secondary calcination is hydrogen.
2. The catalyst according to claim 1, wherein the mass percentage of the active component in the catalyst is 0.1-10%.
3. The catalyst according to claim 2, wherein the mass percentage of the active component in the catalyst is 1-8%.
4. A method for preparing a catalyst according to any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) Dispersing a carrier in a ruthenium precursor solution, and performing ultrasonic treatment to obtain a suspension;
(2) And (2) adding a reducing agent into the suspension obtained in the step (1) to perform a reduction reaction so as to deposit ruthenium metal, thereby obtaining the catalyst.
5. The method according to claim 4, wherein the concentration of the ruthenium precursor solution in the step (1) is 0.001 to 0.1g/mL.
6. The method according to claim 4, wherein the ruthenium precursor in the step (1) is a ruthenium salt.
7. The method according to claim 6, wherein the ruthenium salt comprises any one of ruthenium chloride, ruthenium acetate, or ruthenium nitrate, or a combination of at least two thereof.
8. The method according to claim 4, wherein the time for the ultrasonic treatment in step (1) is 0.5 to 24 hours.
9. The method according to claim 4, wherein the suspension of step (1) has a liquid-solid mass ratio of 10 to 40.
10. The preparation method according to claim 4, wherein the reducing agent in step (2) comprises any one of hydrazine hydrate, sodium formate, formaldehyde, sodium borohydride, potassium borohydride, lithium borohydride or lithium aluminum hydride or a combination of at least two of the above.
11. The method according to claim 4, wherein the time for the reduction reaction in step (2) is 0.5 to 24 hours.
12. The production method according to claim 4, wherein the mass ratio of the reducing agent to the ruthenium precursor in the step (2) is 0.5 to 3.
13. The method for preparing according to any one of claims 4 to 12, characterized in that it comprises the steps of:
(1) Dispersing a carrier in a ruthenium precursor solution with the concentration of 0.001-0.1 g/mL, and performing ultrasonic treatment for 0.5-24 hours to obtain a suspension, wherein the liquid-solid mass ratio of the suspension is (10-40);
the carrier is prepared by calcining any one or the combination of at least two of cyanamide, dicyandiamide, melamine, thiourea, urea or guanidine hydrochloride for two times; or the like, or, alternatively,
the carrier is prepared by mixing any one or combination of at least two of cyanamide, dicyandiamide, melamine, thiourea, urea or guanidine hydrochloride with any one or combination of at least two of chitosan, glucose, sucrose, porous carbon, graphene or graphene oxide and then calcining for two times;
the temperature of the primary calcination is 400-700 ℃, the time is 0.5-5 h, and the atmosphere is air;
the temperature of the secondary calcination is 200-600 ℃, the time is 0.5-4 h, and the atmosphere is hydrogen;
(2) And (2) adding a reducing agent into the suspension obtained in the step (1) to perform a reduction reaction for 0.5-24 h, so as to deposit metal ruthenium, thereby obtaining the catalyst, wherein the mass ratio of the reducing agent to the ruthenium precursor is 0.5-3.
14. Use of the catalyst according to any one of claims 1 to 3, wherein the catalyst is used for synthesizing alicyclic amine by catalytic hydrogenation and saturation of benzene ring-containing amine compound;
the benzene ring-containing amine compound comprises at least one benzene ring, wherein the benzene ring is connected with at least one amino substituent, and the general formula of the benzene ring-containing amine compound is shown as formulas I-VI:
Figure FDA0003936725210000031
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 And R 9 Are respectively H or C1-C4 alkyl, and X is F, cl or Br.
15. The use according to claim 14, wherein the benzene ring-containing amine compound comprises any one of 4,4' -diaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, o-phenylenediamine, p-chloroaniline, or aniline.
16. The use as claimed in claim 14, wherein the initial pressure of the reaction for synthesizing alicyclic amine by catalytic hydrogenation and saturation of benzene ring of the benzene ring-containing amine compound is 0.5-10 MPa, the reaction temperature is 30-200 ℃, and the reaction time is 0.5-4 h.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491904A (en) * 2011-12-20 2012-06-13 常州大学 Application of hydrogenation catalyst to preparation of 1,4-cyclohexanediamine
CN104496943A (en) * 2014-11-28 2015-04-08 林康艺 Method for preparing dihydroxymethyl tetrahydrofuran
CN110252367A (en) * 2019-05-06 2019-09-20 江苏大学 Solvent-thermal method prepares few layer carbonitride load vanadium dioxide catalyst and its desulfurization application
CN112705241A (en) * 2019-10-25 2021-04-27 中国科学院过程工程研究所 Ruthenium-based catalyst, preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491904A (en) * 2011-12-20 2012-06-13 常州大学 Application of hydrogenation catalyst to preparation of 1,4-cyclohexanediamine
CN104496943A (en) * 2014-11-28 2015-04-08 林康艺 Method for preparing dihydroxymethyl tetrahydrofuran
CN110252367A (en) * 2019-05-06 2019-09-20 江苏大学 Solvent-thermal method prepares few layer carbonitride load vanadium dioxide catalyst and its desulfurization application
CN112705241A (en) * 2019-10-25 2021-04-27 中国科学院过程工程研究所 Ruthenium-based catalyst, preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Junya Cao等.Ru/g-C3N4 as an efficient catalyst for selective hydrogenation of aromatic diamines to alicyclic diamines.《RSC Advances》.2020,第10卷(第28期),第16515页. *
Ru/g-C3N4 as an efficient catalyst for selective hydrogenation of aromatic diamines to alicyclic diamines;Junya Cao等;《RSC Advances》;20200425;第10卷(第28期);摘要，第2.2节，第2.4节，第3.5节 *

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