CN111056948B - Process for preparing hexamethylenediamine - Google Patents
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- CN111056948B CN111056948B CN201911296843.XA CN201911296843A CN111056948B CN 111056948 B CN111056948 B CN 111056948B CN 201911296843 A CN201911296843 A CN 201911296843A CN 111056948 B CN111056948 B CN 111056948B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The application discloses a method for preparing hexamethylene diamine, which comprises the steps of introducing a raw material containing hexamethylene dialdehyde into a reactor, and reacting in the presence of ammonia gas, hydrogen gas and a catalyst to generate hexamethylene diamine; wherein the catalyst is an HZSM-5 molecular sieve encapsulated noble metal catalyst. According to the method, metal is encapsulated inside a molecular sieve pore channel, and hexanediamine is prepared by catalyzing hexanedialdehyde through reductive amination, so that the use of a highly toxic raw material adiponitrile is avoided, and the route is clean and environment-friendly.
Description
Technical Field
The application relates to a method for preparing hexamethylene diamine, and belongs to the field of chemistry and chemical engineering.
Background
Hexamethylenediamine is an important organic chemical raw material, and can be used for preparing polyhexamethylene adipamide, also called polyamide 66(PA66) or nylon 66, by a polycondensation reaction with adipic acid.
The production technology of hexamethylenediamine mainly comprises an adiponitrile method, a hexanediol method and a caprolactam method. Currently, hexamethylenediamine is almost exclusively prepared by hydrogenation of adiponitrile, which is produced by processes such as adipic acid catalytic amination, acrylonitrile electrolytic dimerization and butadiene. Domestic adiponitrile completely depends on import, the price of the adiponitrile is always high, the economic benefit and international market competitiveness of the nylon industry in China are seriously affected, and the development of the nylon 66 and related industries in China is restricted. Therefore, the development of a new technology for preparing hexamethylene diamine is a problem to be solved urgently in the field of domestic chemical industry.
CN108084035A discloses a method for preparing hexanediamine by directly hydrogenating adiponitrile under the alkali-free condition, wherein an alkaline earth metal oxide or rare earth metal oxide modified aluminum trioxide supported metal nickel catalyst prepared by a coprecipitation method is used for preparing hexanediamine by hydrogenating an adiponitrile ethanol solution with a certain concentration. CN104262168B discloses a method for preparing hexamethylenediamine by aminating hexanedial with nickel-based hydrogenation catalyst loaded on silica carrier.
From the literature and the technology which are available at present, the raw material adiponitrile in the industrialized adiponitrile hydrogenation preparation route of the hexamethylenediamine is high in toxicity, dependent on import and high in price. The development of a new green hexamethylenediamine preparation process is of great significance. Therefore, the development of a catalyst with good catalyst activity and target product selectivity is the key for realizing a green new process of the hexamethylene diamine.
Disclosure of Invention
According to one aspect of the application, the method for preparing the hexanediamine from the hexanedialdehyde is provided, the precious metal is encapsulated inside the pore canal of the molecular sieve, the hexanediamine is prepared by catalyzing the hexanedialdehyde through reductive amination, the use of a highly toxic raw material adiponitrile is avoided, and the route is clean and environment-friendly.
The method for preparing hexamethylene diamine based on the catalyst-catalyzed hexamethylene dialdehyde comprises the following steps:
introducing a raw material containing adipaldehyde into a reactor, and reacting in the presence of ammonia gas, hydrogen gas and a catalyst to generate hexamethylenediamine; wherein the catalyst is an HZSM-5 molecular sieve encapsulated noble metal catalyst.
Optionally, the molar ratio of ammonia to adipic dialdehyde is 5-60: 1, and the molar ratio of hydrogen to adipic dialdehyde is 1-80: 1. preferably, the reaction temperature is 80-150 ℃; the reaction pressure is 5-10 Mpa.
Optionally, the noble metal is selected from at least one of Ru, Rh and Pd;
the mass content of the noble metal in the catalyst is 0.1-6.0% of the total mass of the catalyst.
Alternatively, the upper limit of the mass content of the noble metal in the catalyst may be selected from 6%, 5.83%, 5.63%, 3.84%, 2.82%, 2.7%, 0.952%, 0.93%, 0.92%, 0.48% or 0.5%, and the lower limit may be selected from 5.83%, 5.63%, 3.84%, 2.82%, 2.7%, 0.952%, 0.93%, 0.92%, 0.48% or 0.085%.
Optionally, the reaction conditions include:
the reaction temperature is 80-200 ℃;
the reaction pressure is 1-20 Mpa.
Preferably, the reaction temperature is 80-150 ℃; the reaction pressure is 5-10 Mpa.
Optionally, the catalyst has a hierarchical pore structure;
optionally, the mass ratio of the used amount of the catalyst to the adipic dialdehyde is 0.1-0.5: 1.
Optionally, the method for obtaining the HZSM-5 molecular sieve-encapsulated noble metal catalyst comprises:
and (3) in-situ crystal transformation is carried out to obtain a ZSM-5 molecular sieve for packaging the noble metal, and then roasting and ammonium exchange are carried out to obtain the HZSM-5 molecular sieve packaging noble metal catalyst.
Optionally, the in-situ transcrystalizing obtains a noble metal encapsulated ZSM-5 molecular sieve comprising:
(1) placing the HBeta molecular sieve loaded with noble metal in a template agent solution, and impregnating and drying to obtain the HBeta molecular sieve loaded with noble metal and adsorbed with the template agent;
(2) and (2) crystallizing a mixture of an alkali source, water and the noble metal-loaded HBeta molecular sieve adsorbed with the template in the step (1) to obtain the noble metal-encapsulated ZSM-5 molecular sieve.
By dipping the silicon-aluminum molecular sieve loaded with noble metal into the template solution and drying, the template existing in the molecular sieve can effectively slow down the dissolution of the molecular sieve, so that the dissolution speed and the crystallization speed are more coordinated, and compared with the method of directly adding the template into the crystallization liquid, the method can obtain higher yield, ensure that the transition metal is uniformly dispersed in the pore canal of the molecular sieve, avoid the transition metal from being separated, and ensure the content of the transition metal. Not only ensures that the metal is uniformly dispersed in the molecular sieve pore canal, but also avoids the metal from being separated, and ensures the metal content.
Optionally, the templating agent is selected from TPAOH, TPABr, or ethanol.
In the embodiment of the invention, the template is not limited to the above, and any template with the same or similar functions can be selected.
Optionally, the template agent and SiO contained in the HBeta molecular sieve loaded with noble metal2The molar ratio of (A) to (B) is 0.10 to 0.40.
Optionally, the impregnation conditions in step (1) include:
the dipping temperature is 20-30 ℃;
the dipping time is 1-3 h.
Optionally, the drying conditions in step (1) comprise:
the drying time is 30-100 ℃;
the drying time is 12-16 h.
Optionally, the mass loading of the noble metal in the noble metal-loaded HBeta molecular sieve in the step (1) is 0.1-6.0%. The loading amount in the embodiment of the invention is based on the total mass of the catalyst.
Optionally, in the step (2), the alkali source is sodium hydroxide, potassium hydroxide or ammonia water, and the solvent is water or deionized water;
SiO in the transition metal loaded HBeta molecular sieve adsorbed with the template agent2The mass ratio of the alkali source to the water is 1 (0.10-0.50) to 2-40.
Optionally, the crystallization conditions in step (2) include:
the crystallization temperature is 80-200 ℃;
the crystallization time is 2-10 h.
Optionally, in the step (1), the noble metal salt precursor solution is impregnated on the HBeta molecular sieve by an isometric impregnation method, and the HBeta molecular sieve loaded with the noble metal is obtained by drying and roasting in a reducing atmosphere;
the noble metal salt precursor is selected from RuCl3·3H2O，RhCl3·3H2O，PdCl2。
Optionally, the ammonium exchange specifically includes the following steps:
and (3) carrying out ion exchange on the ZSM-5 molecular sieve without the encapsulated noble metal by adopting a solution containing ammonium ions, and then roasting.
Optionally, the ion exchange conditions comprise:
the concentration of ammonium ions in the solution containing ammonium ions is 0.2-1 mol/L;
the solid-liquid weight ratio is 0.1-0.5: 1;
the temperature of the solution containing ammonium ions is 60-80 ℃;
the exchange time is 1-12 h.
Optionally, the calcination conditions after ion exchange include:
the roasting temperature is 400-600 ℃;
the roasting time is 3-6 h.
Optionally, the ion exchange is repeated 1-3 times.
Optionally, the reactor is a high pressure autoclave.
Optionally, the hexanedial is mixed with an organic solvent and then introduced into the reactor; the organic solvent is at least one selected from methanol, ethanol and isopropanol.
In one embodiment, a method of making hexamethylenediamine from hexamethylenedialdehyde comprises:
in a high-pressure reaction kettle, carrying out reductive amination reaction in the presence of a catalyst, ammonia, hydrogen and a solvent to generate hexamethylenediamine, wherein the reaction temperature is 80-200 ℃, the reaction pressure is 1-20 Mpa, and the catalyst is a noble metal catalyst encapsulated by a molecular sieve.
Preferably, the reaction temperature is 80-150 ℃.
Preferably, the reaction pressure is 5-10 MPa.
In the preparation method of the hexamethylene diamine, the molar ratio of ammonia to the hexamethylene dialdehyde is 5-60: 1, the molar ratio of hydrogen to adipaldehyde is 1-80: 1.
in the preparation method of the hexamethylene diamine, a metal catalyst packaged by a molecular sieve is adopted, and the metal is one or two of Ru, Rh and Pd. The content of the metal active component is 0.1-6.0%.
The molecular sieve encapsulated metal catalyst is prepared by adopting an in-situ crystal transformation method, and the preparation method comprises the following steps:
(a) putting the HBeta molecular sieve into a metal salt solution to be soaked for 24 hours at room temperature by adopting an isometric soaking method,
loading metal on HBeta molecular sieve, drying in 100 deg.C oven for 12 hr, and drying in H2Reducing for 4h at 500 ℃ in the atmosphere to obtain the M/HBeta molecular sieve;
(b) putting the metal-loaded HBeta molecular sieve (M/HBeta) in a TPAOH solution, soaking for 2h at room temperature, and drying in an oven at 100 ℃ for 12h to obtain the M/HBeta molecular sieve with TPAOH adsorbed in pore channels;
(c) SiO in the M/HBeta molecular sieve of the TPAOH obtained in the step b2Mixing the metal and sodium hydroxide with deionized water according to the mass ratio of 1 (0.10-0.50) to 2-40 to prepare a system, and crystallizing at 80-100 ℃ for 2-10 hours to obtain a metal @ ZSM-5 molecular sieve;
(d) roasting the metal @ ZSM-5 molecular sieve prepared in the step c to remove a template agent, and then carrying out ion exchange in an ammonium nitrate solution to obtain a hydrogen type molecular sieve, wherein the concentration of the solution is 0.2-1 mol/L, the solid-liquid weight ratio is 0.1-0.5: 1, the temperature of the solution is 60-80 ℃, the time is 1-12 hours, and the ion exchange times are 2-4 times; and after exchange, performing centrifugal separation on the solid sample, washing with deionized water, drying in an air atmosphere at 80-120 ℃, and roasting in an air atmosphere at 500 ℃ for 3-6 hours to obtain the hydrogen type molecular sieve, namely the catalyst.
The metal salt solution can be a metal salt precursor can be RuCl3·3H2O，RhCl3·3H2O，PdCl2。
The solvent is one of methanol, ethanol and isopropanol.
The "metal @ ZSM-5 molecular sieve" described in the examples of the present invention does not mean that the metal and the ZSM-5 molecular sieve form a core-shell structure, but means that the ZSM-5 molecular sieve encapsulates the metal, and in the following description of forms similar to A @ B, A means the encapsulated metal and B means the molecular sieve.
The beneficial effects that this application can produce include:
1) the precious metal catalyst encapsulated by the ZSM-5 molecular sieve is used for catalyzing the adipic dialdehyde to prepare the hexamethylene diamine through reductive amination, so that the use of a virulent raw material adiponitrile is avoided, and the route is clean and environment-friendly;
2) according to the catalyst, the noble metal is encapsulated inside the pore canal of the molecular sieve, and the selectivity of a target product and the stability of the catalyst are effectively improved by utilizing the confinement effect of the molecular sieve;
3) the catalyst provided by the invention has economic advantages and industrial application prospects.
Drawings
Figure 1 shows the XRD spectrum of the HBeta molecular sieve of example 1.
FIG. 2 shows the XRD pattern of the Ru @ ZSM-5 molecular sieve of example 1.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
Wherein: HBeta molecular sieves were purchased from southern catalyst factories;
SiO in HBeta molecular sieve2The mass content was analyzed by ICP-OES.
The analytical methods and conversion, selectivity in the examples were calculated as follows:
analysis was performed using an Agilent7890 gas chromatograph with an autosampler. After the reaction is finished, adding n-octylamine into the reaction solution as an internal standard, and carrying out quantitative analysis by an internal standard method.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
conversion of adipaldehyde [ (adipaldehyde carbon mole number in feed) - (adipaldehyde carbon mole number in discharge) ]/(adipaldehyde carbon mole number in feed) × 100%
Hexamethylenediamine selectivity (the mole number of hexamethylenediamine carbon in the discharged material) ÷ (the total mole number of all carbon-containing products in the discharged material) × 100%
Hexamethylenediamine yield (moles of hexamethylenediamine carbon in the discharge) ÷ (moles of converted hexamethylenedialdehyde carbon) × 100%
EXAMPLE 1 preparation of Metal @ molecular Sieve catalyst
(1) Adding 0.03 gGluCl3·3H2Dissolving O in water, diluting to 12mL, and taking 10g HBeta molecular Sieve (SiO)2/Al2O3Molar ratio of 800, SiO298.9 percent of mass content), loading the Ru element on HBeta by an isometric impregnation method, drying in a 100 ℃ oven for 12H, and then drying in H2Reducing for 4h at 500 ℃ in the atmosphere to obtain a negative metal Ru/HBeta molecular sieve;
(2) placing the Ru/HBeta molecular sieve loaded with metal in 15mL of TPAOH aqueous solution with the mass fraction of 35.0%, soaking at room temperature for 2h, and drying in a 100 ℃ oven for 12h to obtain the/HBeta molecular sieve with TPAOH adsorbed in pore channels;
(3) mixing the HBeta molecular sieve with TPAOH adsorbed in the pore channel with 0.60g of sodium hydroxide and 20mL of deionized water, and crystallizing at 90 ℃ for 6 hours to obtain a Ru @ ZSM-5 molecular sieve;
(4) roasting the Ru @ ZSM-5 molecular sieve at 500 ℃ for 4 hours to remove a template agent TPAOH, and performing ion exchange in 1.0mol/L ammonium nitrate solution to obtain a hydrogen type molecular sieve, wherein the solid-liquid weight ratio during ion exchange is 1: 10, the solution temperature is 80 ℃, the ion exchange time is 2 hours each time, and the ion exchange is carried out for 3 times;
(5) and after exchange, carrying out centrifugal separation and deionized water washing on a solid sample, drying in an air atmosphere at 100 ℃, and roasting for 4 hours in an air atmosphere at 500 ℃ to obtain a hydrogen type molecular sieve HZSM-5 molecular sieve packaging Ru catalyst which is marked as 0.1Ru @ ZSM-5.
Examples 2-10 preparation of Metal @ molecular Sieve catalysts
M @ ZSM-5 was prepared by the same procedure as in example 1, and the kind and loading of the metal were adjusted by changing the kind and concentration of the metal salt solution, and the specific synthesis conditions are shown in Table 1. And testing the mass content of the metal in the M @ ZSM-5 by adopting ICP-OES.
TABLE 1 specific Synthesis conditions for the examples
In the table, in the catalyst nA @ ZSM-5, A represents a noble metal, ZSM-5 is HZSM-5, W (%) represents the mass content of the metal in M @ ZSM-5, and n represents the mass loading of the noble metal in the M/HBeta molecular sieve.
Examples 1-10 metal @ molecular sieve catalyst characterization
FIG. 1 is an XRD spectrum of the HBeta molecular sieve used in example 1; the catalysts obtained in examples 1-10 are ZSM-5 molecular sieves, typically representing the XRD pattern of the catalyst in example 1 as shown in FIG. 2. The XRD spectrums of the catalysts obtained in the examples 2-10 are similar to those of the catalyst obtained in the example 1, namely, the positions and the shapes of diffraction peaks are basically the same, and the relative peak intensity fluctuates within +/-5% according to the change of synthesis conditions, which shows that the catalysts obtained in the examples 2-10 have the characteristics of a ZSM-5 structure.
EXAMPLES 11-20 evaluation of reactivity of Metal @ molecular Sieve catalysts
Adding 5.0g of catalyst into a quartz tube, introducing reducing gas into the quartz tube at the flow rate of 30mL/min, and reducing the catalyst at 400 ℃ for 4H, wherein the reducing gas is H2/N21/4 by volume ratio. After the reduction is finished, the temperature is reduced to room temperature, and the catalyst is taken out and added into a 300ml high-pressure reaction kettle.
At room temperature, 20g of adipaldehyde and 100g of methanol are uniformly mixed, added into the 300mL high-pressure reaction kettle, sealed, replaced by nitrogen for three times, injected with 29.75g of liquid ammonia through a high-pressure pump, filled with hydrogen until the pressure in the kettle is 4.0Mpa, raised to 120 ℃, at the moment, the pressure reaches 7.5MPa, quickly cooled after reacting for 2 hours, centrifugally separated out the catalyst, added with a certain amount of n-octylamine, and analyzed by gas chromatography.
TABLE 2 reactivity of catalysts prepared in examples 1-10
As can be seen from Table 2, the catalyst provided by the embodiments of the present invention shows excellent selectivity to hexamethylene diamine in the reaction of preparing hexanediamine by reductive amination of hexanediamine, wherein the selectivity of hexanediamine can reach 81.52% at most, and the conversion rate of hexanediamine can reach 100% at most; when the metal is Ru and the mass loading of the metal is 1-3%, the selectivity of the hexamethylene diamine can reach more than 78.31%, and the conversion rate of the hexamethylene dialdehyde can reach 100%.
EXAMPLES 21-28 evaluation of reactivity of Metal @ molecular Sieve catalysts
Adding 5.0g of catalyst into a quartz tube, introducing reducing gas into the quartz tube at the flow rate of 30mL/min, and reducing the catalyst at 400 ℃ for 4H, wherein the reducing gas is H2/N21/4 by volume ratio. After the reduction is finished, the temperature is reduced to room temperature, and the catalyst is taken out and added into a 300ml high-pressure reaction kettle.
At room temperature, 20g of adipaldehyde and 100g of methanol are uniformly mixed, added into a 300mL high-pressure reaction kettle, sealed, subjected to nitrogen replacement for three times, injected with liquid ammonia through a high-pressure pump, filled with hydrogen to the pressure in the kettle, heated to a certain temperature, reacted for 2 hours, rapidly cooled, centrifugally separated to obtain a catalyst, added with a certain amount of n-octylamine, and analyzed by gas chromatography.
TABLE 3 results of the reactions of examples 21 to 28
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (8)
1. A method for preparing hexamethylene diamine is characterized in that raw materials containing hexamethylene dialdehyde are introduced into a reactor and react in the presence of ammonia gas, hydrogen gas and a catalyst to generate hexamethylene diamine; wherein the catalyst is an HZSM-5 molecular sieve encapsulated noble metal catalyst;
the method for obtaining the HZSM-5 molecular sieve encapsulated noble metal catalyst comprises the following steps:
carrying out in-situ crystal transformation to obtain a ZSM-5 molecular sieve for encapsulating noble metal, and then roasting and carrying out ammonium exchange to obtain the HZSM-5 molecular sieve encapsulated noble metal catalyst;
the in-situ crystal transformation is carried out to obtain the ZSM-5 molecular sieve for encapsulating the noble metal, and the method comprises the following steps:
(1) placing the HBeta molecular sieve loaded with noble metal in a template agent solution, and impregnating and drying to obtain the HBeta molecular sieve loaded with noble metal and adsorbed with the template agent;
(2) and (2) crystallizing a mixture of an alkali source, water and the noble metal-loaded HBeta molecular sieve adsorbed with the template in the step (1) to obtain the noble metal-encapsulated ZSM-5 molecular sieve.
2. The method according to claim 1, wherein the molar ratio of ammonia gas to adipaldehyde is 5-60: 1, the molar ratio of hydrogen to adipaldehyde is 1-80: 1.
3. the method according to claim 1, wherein the noble metal is selected from at least one of Ru, Rh, Pd; the mass content of the noble metal in the catalyst is 0.1-6.0%.
4. The method of claim 1, wherein the reaction conditions comprise:
the reaction temperature is 80-200 ℃;
the reaction pressure is 1-20 Mpa.
5. The method according to claim 4, wherein the reaction temperature is 80 to 150 ℃.
6. The method according to claim 4, wherein the reaction pressure is 5 to 10 MPa.
7. The method of claim 1, wherein the reactor is an autoclave.
8. The method of claim 1, wherein the feedstock further comprises an organic solvent; the organic solvent is at least one selected from methanol, ethanol and isopropanol.
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