CN111116377B - Method for preparing hexamethylene diamine - Google Patents
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- CN111116377B CN111116377B CN201911296847.8A CN201911296847A CN111116377B CN 111116377 B CN111116377 B CN 111116377B CN 201911296847 A CN201911296847 A CN 201911296847A CN 111116377 B CN111116377 B CN 111116377B
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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
- B01J29/46—Iron group metals or copper
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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
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Abstract
The application discloses a method for preparing hexamethylene diamine, which comprises the step of reacting a raw material containing hexamethylene dialdehyde in the presence of ammonia gas, hydrogen gas and a catalyst to generate the hexamethylene diamine, wherein the catalyst is an HZSM-5 molecular sieve-encapsulated transition metal catalyst. According to the method, transition 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 from hexamethylene dialdehyde, and belongs to the field of chemical engineering.
Background
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.
The production of hexamethylene diamine is mainly monopolized by some large-scale transnational companies, the total of three members of Invida, Pasteur and Oshende accounts for 74% of the global productivity, the hexamethylene diamine is in the high oligopolistic industry, and the global productivity of China Mars, ranked on the fourth place, accounts for 9%. The manufacturers capable of producing hexanediamine in China only comprise Liaoyang petrochemical company in China and Shenma group in China. In the Liaoyang petrochemical industry, adiponitrile is produced by an adipic acid ammoniation method, and production is stopped due to the problems of long process route, low product yield and the like. 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.
CN109647419A discloses a method for preparing hexanediamine by using nickel-based catalyst loaded on alumina as active component and catalyzing adiponitrile hydrogenation in a tank reactor. CN106807377A discloses a method for synthesizing hexamethylenediamine under the condition of hydrogenation by using a catalyst which takes one or more of Ni or Co main active components Fe, Cu, Ru, Re, K, Zn, B and other metals or oxides as an auxiliary agent to catalyze the ammoniation reaction of hexanediol or aminohexanol or hexanediol/aminohexanol mixture. 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 is provided, the hexanediamine is prepared by adopting the HZSM-5 molecular sieve to encapsulate a transition metal catalyst to catalyze the hexanediamine to carry out 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 comprises the following steps: reacting a raw material containing adipaldehyde in the presence of ammonia gas, hydrogen gas and a catalyst to generate hexamethylenediamine; wherein the catalyst is an HZSM-5 molecular sieve-encapsulated transition metal catalyst.
Optionally, the conditions of the reaction 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 3-10 Mpa.
Optionally, the molar ratio of ammonia to adipaldehyde is 5-60: 1, the molar ratio of hydrogen to adipaldehyde is 5-60: 1.
optionally, the transition metal is selected from at least one of Ni, Co and Cu;
the transition metal loading is 3.0-40.0%.
Alternatively, the transition metal may be supported in the catalyst at an upper limit selected from 40%, 29.65%, 25.96%, 25.69%, 20%, 15%, 14.93%, 14.35%, 13.98%, 9.62%, 9.58% or 8.52% and a lower limit selected from 29.65%, 25.96%, 25.69%, 20%, 15%, 14.93%, 14.35%, 13.98%, 9.62%, 9.58% or 8.52% or 4.35% by total mass of the catalyst.
Optionally, the method for obtaining the HZSM-5 molecular sieve-encapsulated transition metal catalyst comprises:
and (3) carrying out in-situ crystal transformation to obtain a ZSM-5 molecular sieve for encapsulating the transition metal, and then roasting and carrying out ammonium exchange to obtain the HZSM-5 molecular sieve encapsulated transition metal catalyst.
Optionally, the in-situ transcrystalizing to obtain the transition metal-encapsulated ZSM-5 molecular sieve comprises:
(1) putting the transition metal loaded HBeta molecular sieve into a template agent solution, and impregnating and drying to obtain the transition metal loaded HBeta molecular sieve adsorbed with the template agent;
(2) crystallizing a mixture containing an alkali source, water and the transition metal loaded HBeta molecular sieve adsorbed with the template in the step (1) to obtain the transition metal encapsulated ZSM-5 molecular sieve.
By dipping the HBeta molecular sieve loaded with the transition 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 molecular sieve pore canal, avoid the transition metal from being separated, and ensure the content of the transition metal.
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 addition amount of the template agent is equal to SiO contained in the transition metal-loaded HBeta molecular sieve2The 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 amount of the transition metal in the transition metal-loaded HBeta molecular sieve in the step (1) is 3.0-40.0%, and preferably 5-30%. The loading amount in the embodiment of the invention is based on the total mass of the catalyst.
Optionally, the alkali source in step (2) is sodium hydroxide;
SiO in the transition metal-loaded HBeta molecular sieve2The mass ratio of the alkali source to the water is 1 (0.10-0.50) to 2-40.
Alternatively, SiO in the transition metal-loaded HBeta molecular sieve2The upper limit of the mass ratio of the alkali source to the alkali source can be selected from 1:0.06, 1:0.07, 1:0.072, 1:0.074, 1:0.075, 1:0.08 or 1:0.083, and the lower limit can be selected from 1:0.07, 1:0.072, 1:0.074, 1:0.075, 1:0.08, 1:0.083 or 1: 0.2.
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 transition metal salt precursor solution is impregnated on the HBeta molecular sieve by an isometric impregnation method, and the HBeta molecular sieve loaded with the transition metal is obtained after drying and roasting in a reducing atmosphere;
the transition metal salt is at least one selected from acetate, oxalate, nitrate, sulfate and chloride of transition metal.
Optionally, the ammonium exchange specifically includes the following steps:
and (3) carrying out ion exchange on the ZSM-5 molecular sieve for packaging the transition 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.
In one embodiment, a method for preparing hexamethylenediamine comprises:
in a fixed bed reactor, carrying out reductive amination reaction in the presence of a molecular sieve-encapsulated metal catalyst, ammonia and hydrogen to generate hexamethylenediamine, wherein the reaction temperature is 80-200 ℃, and the reaction pressure is 1-20 Mpa.
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 gas to the hexamethylene dialdehyde is 5: 1-20, wherein the molar ratio of hydrogen to adipaldehyde is 1-30: 1.
in the preparation method of the hexamethylene diamine, the mass space velocity of the hexamethylene dialdehyde is 0.5-10.0 h-1。
In the preparation method of the hexamethylene diamine, a metal catalyst packaged by a molecular sieve is adopted, the transition metal is one or two of Ni, Co and Cu, and the content of the active components of the transition metal is 5.0-50.0% by total mass of the catalyst.
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) soaking HBeta molecular sieve in metal salt solution at room temperature for 24 hr by isovolumetric soaking method, loading metal on HBeta molecular sieve, drying in oven at 100 deg.C for 12 hr, and placing in H2Reducing for 4h at 500 ℃ in the atmosphere to obtain the M/HBeta molecular sieve;
(b) placing a metal-loaded HBeta molecular sieve (M/HBeta molecular sieve) 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 (0.06-0.50) 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 one of acetate, oxalate, nitrate, sulfate and chloride.
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 transition metal catalyst encapsulated by the ZSM-5 molecular sieve is adopted to catalyze the hexanediamine to prepare the hexanediamine 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, metal is encapsulated inside a molecular sieve pore channel, and the selectivity of a target product and the stability of the catalyst are effectively improved by utilizing the confinement effect of a 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 Ni @ 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.
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) 2.48gNi (NO)3)2·6H2Dissolving 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 Ni 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 metal-loaded Ni/HBeta molecular sieve;
(2) putting the Ni/HBeta molecular sieve loaded with metal into 15mL of TPAOH aqueous solution with the mass fraction of 35.0%, soaking for 2h at room temperature, and drying in a drying oven at 100 ℃ 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 Ni @ ZSM-5 molecular sieve;
(4) roasting the Ni @ ZSM-5 molecular sieve at 500 ℃ for 4h to remove a template agent TPAOH, and performing ion exchange in 1.0mol/L ammonium nitrate solution to obtain a hydrogen type molecular sieve; the conditions of ion exchange were: the solid-liquid weight ratio 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) 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 an HZSM-5 molecular sieve packaging Ni catalyst which is marked as 5.0Ni @ ZSM-5;
examples 2-10 preparation of transition 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.
TABLE 1 specific Synthesis conditions for the examples
In the table, in the catalyst nA @ ZSM-5, A represents a transition metal, ZSM-5 is abbreviated as HZSM-5, n represents the mass loading of the transition metal in M/Hbeta, and W (%) represents the mass content of the metal in M @ ZSM-5.
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
Filling 2.0g of the catalyst into a stainless steel fixed bed reactor with the inner diameter of 10mm and the length of 300mm, filling quartz sand at two ends of the catalyst, firstly introducing reducing gas at the flow rate of 30mL/min, and carrying out reduction treatment on the catalyst for 4 hours at 400 ℃, wherein the reducing gas consists of H2/N2Volume ratio 1/4.
After the reduction is finished, the temperature of the reactor is reduced to 130 ℃, the reaction pressure is increased to 6.0Mpa, and H is respectively introduced into the reactor2Liquid ammonia and hexanedial are subjected to reductive amination reaction, wherein the liquid ammonia and the hexanedial are respectively injected into a reaction system through a high-pressure trace feed pump, and the mass space velocity of the hexanedial is 1.0h-1，H2:NH3When the reaction time was 10 hours, the reaction results were shown in Table 2, by taking samples and analyzing the samples by gas chromatography, while the ratio of adipic dialdehyde was 15:30: 1.
TABLE 2 reactivity of catalysts prepared in examples 1-10
As can be seen from Table 2, the catalyst provided by each embodiment of the invention has excellent selectivity on hexamethylene diamine in the reaction of preparing hexanediamine by reductive amination of hexanediamine, wherein the selectivity of the hexanediamine can reach 93.4% at most, and the conversion rate of the hexanediamine can reach 99.8% at most; when the metal mass loading is 15-30% and the catalyst crystallization temperature is 90-100 ℃, the selectivity of the hexamethylene diamine can reach more than 91.4%, and the yield of the hexamethylene diamine can reach more than 85.64%.
EXAMPLES 21-28 evaluation of reactivity of Metal @ molecular Sieve catalysts
Filling 2.0g of the catalyst into a small-sized fixed bed reactor, filling quartz sand at two ends of the catalyst, firstly introducing reducing gas at the flow rate of 30mL/min, and carrying out reduction treatment on the catalyst for 4 hours at 400 ℃, wherein the reducing gas consists of H2/N2Volume ratio 1/4.
After the reduction is finished, the temperature of the reactor and the reaction are adjusted to the reaction condition, and the reaction is respectively carried out on the reactorIs internally introduced with H2And liquid ammonia and hexanedial are subjected to reductive amination, wherein the liquid ammonia and the hexanedial are respectively injected into a reaction system through a high-pressure trace feed pump, the reaction is carried out for 10 hours, the sampling is carried out by adopting gas chromatography, and the specific reaction conditions, the material ratio and the reaction results are listed in Table 3.
Table 3 reaction performance of example 3 catalyst preparation
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 (7)
1. A method for preparing hexamethylene diamine is characterized in that raw materials containing hexamethylene dialdehyde 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 transition metal catalyst;
the transition metal is selected from at least one of Ni, Co and Cu;
the method for obtaining the HZSM-5 molecular sieve encapsulated transition metal catalyst comprises the following steps:
carrying out in-situ crystal transformation to obtain a ZSM-5 molecular sieve for encapsulating transition metal, and then roasting and carrying out ammonium exchange to obtain the HZSM-5 molecular sieve encapsulated transition metal catalyst;
the in-situ crystal transformation method for obtaining the ZSM-5 molecular sieve for encapsulating the transition metal comprises the following steps:
(1) putting the transition metal loaded HBeta molecular sieve into a template agent solution, and impregnating and drying to obtain the transition metal loaded HBeta molecular sieve adsorbed with the template agent;
(2) crystallizing a mixture containing an alkali source, water and the transition metal loaded HBeta molecular sieve adsorbed with the template in the step (1) to obtain the transition metal encapsulated ZSM-5 molecular sieve.
2. The method of claim 1, wherein the reaction conditions comprise:
the reaction temperature is 80-200 ℃;
the reaction pressure is 1-20 Mpa.
3. The method according to claim 2, wherein the reaction temperature is 80 to 150 ℃.
4. The method according to claim 2, wherein the reaction pressure is 3 to 10 MPa.
5. The method according to claim 1, wherein the molar ratio of ammonia gas to adipaldehyde is 5-60: 1.
6. the method according to claim 1, wherein the molar ratio of hydrogen to adipaldehyde is 5-60: 1.
7. the method according to claim 1, wherein the transition metal is supported at 3.0 to 40.0%.
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