CN111330629B - M-xylylenediamine hydrogenation catalyst, and preparation method and application thereof - Google Patents
M-xylylenediamine hydrogenation catalyst, and preparation method and application thereof Download PDFInfo
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- CN111330629B CN111330629B CN202010267205.1A CN202010267205A CN111330629B CN 111330629 B CN111330629 B CN 111330629B CN 202010267205 A CN202010267205 A CN 202010267205A CN 111330629 B CN111330629 B CN 111330629B
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- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
Abstract
The invention provides a catalyst for synthesizing 1, 3-cyclohexyldimethylamine by m-xylylenediamine hydrogenation and a preparation method thereof. The catalyst consists of a carrier, an active component and an auxiliary agent which are attached to the carrier; the active component is composed of one or more of metal Rh, Pt, Pd, Ir, Au, Ag, Ni and Re and noble metal Ru; the auxiliary agent consists of an auxiliary agent I and an auxiliary agent II, wherein the auxiliary agent I consists of metal Eu and metal Yb, the auxiliary agent II is selected from one or more of metal Li, Na, k, Cu, Co, Fe, Zn, Mn, La and Ce, and the carrier is a molecular sieve modified by a metal compound. Compared with the prior art, the catalyst can obtain higher raw material conversion rate and 1, 3-cyclohexyldimethylamine selectivity under lower reaction temperature and pressure, higher substrate concentration and reaction space velocity, has stable performance and long service life, can obviously improve the production efficiency and reduce the production cost, and is beneficial to industrial application.
Description
Technical Field
The invention relates to a hydrogenation catalyst and a preparation method thereof, in particular to a catalyst for synthesizing 1, 3-cyclohexyldimethylamine by hydrogenation of m-xylylenediamine and a preparation method thereof, belonging to the technical field of hydrogenation catalysts.
Background
M-xylylenediamine is used as an epoxy hardener, but has a high freezing point (a freezing point of 14.1 ℃), and its use is limited in low-temperature environments, particularly in cold winter. The hydrogenation is carried out to convert the cyclohexane into 1, 3-cyclohexyldimethylamine, the solidifying point (minus 25 ℃) is greatly reduced, and the cyclohexane has the advantages of high low-temperature solidifying activity, low toxicity and the like, and is widely applied to the fields of crack sealing agents, automobile composite materials and the like.
The prior art for synthesizing 1, 3-cyclohexyldimethylamine by hydrogenation of m-xylylenediamine mainly reports as follows:
CN 102690203A, using 5% Ru-1% Pd/Al 2 O 3 Taking liquid ammonia as a solvent, charging hydrogen into a reactor to 10MPa under the condition that the mass concentration of a substrate is 20 percent and the dosage of the catalyst is 0.2 times of the mass of m-xylylenediamine, then heating to 130 ℃, and reacting for 10 hours at the temperature to obtain the product with the raw material conversion rate of 99.9 percent and the selectivity of 1, 3-cyclohexyldimethylamine of 97.3 percent. Although the conversion rate of the obtained raw materials and the selectivity of the product are high, the technology has the advantages of large catalyst consumption and high cost, and the high-temperature high-pressure batch process is adopted by taking liquid ammonia as a solvent, so that the safety risk is high, and the industrial amplification is not facilitated.
In patent CN 109772312a, 4% Ru/hydrotalcite is used as a catalyst, and lithium hydroxide is used to modify the catalyst, tetrahydrofuran is used as a solvent, and under the conditions of a substrate mass concentration of 3.67%, a catalyst dosage of 0.22 times of the mass of m-xylylenediamine, a reaction temperature of 130 ℃, and a pressure of 5MPa, the conversion rate of the obtained raw material reaches 100%, and the selectivity of 1, 3-cyclohexyldimethylamine reaches 96.1%. The main problems of the technology are that the concentration of the substrate is low, the production efficiency of a reactor with unit volume is low, the energy consumption of solvent separation is high, and the lithium hydroxide is used for modifying the catalyst and is difficult to apply stably.
US5741928 using 2% Ru/Al 2 O 3 The catalyst is subjected to fixed bed continuous hydrogenation, liquid ammonia, 1, 3-cyclohexyldimethylamine or micromolecule organic amine such as diethylamine, triethylamine and the like or a mixture of the diethylamine and alcohols are used as a solvent, the mass concentration of a substrate is 10-15%, the reaction temperature is about 120 ℃, the reaction pressure is 10MPa, and the mass space velocity of m-xylylenediamine is 0.17h -1 Then, the conversion rate of the obtained raw material reaches 100%, and the yield of the 1, 3-cyclohexyldimethylamine is about 95%. The method takes liquid ammonia or micromolecular organic amine as a reaction solvent, and hydrogenation is carried out at a lower substrate concentration and mass airspeed, so that the problems of low production efficiency, high energy consumption and the like exist.
In summary, the main problems of the prior art are: (1) the meta-xylylenediamine has low mass space velocity, so that the catalyst consumption is large and the investment cost is high. In addition, under the condition of an intermittent process, the problem of long filtering time of reaction mother liquor and the like possibly caused by the larger using amount of the catalyst affects the production efficiency; (2) the concentration of the reaction substrate is low, so that the production efficiency of the reactor in unit volume is low, the energy consumption of solvent separation is high, and the production cost is increased; (3) the reaction conditions are harsh, in order to obtain high yield of the 1, 3-cyclohexyldimethylamine, liquid ammonia or other micromolecule organic amines and the like are generally adopted as reaction solvents, or inorganic bases are utilized to modify the catalyst, hydrogenation reaction is carried out at high temperature and high pressure, the safety risk is high, material leakage is easy to occur, and environmental pollution is caused.
Disclosure of Invention
One of the purposes of the present invention is to overcome the above problems and provide a catalyst for synthesizing 1, 3-cyclohexyldimethylamine by hydrogenation of m-xylylenediamine, which has the advantages of high activity, good selectivity and long service life.
Another object of the present invention is to provide a method for preparing the above catalyst.
The invention further aims to provide the application of the catalyst in the synthesis of 1, 3-cyclohexyldimethylamine by hydrogenation of m-xylylenediamine, and the catalyst can obtain higher raw material conversion rate and 1, 3-cyclohexyldimethylamine selectivity under lower reaction temperature and pressure, higher substrate concentration and reaction space velocity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a catalyst for synthesizing 1, 3-cyclohexyldimethylamine by hydrogenating m-xylylenediamine comprises a carrier, and an active component and an auxiliary agent which are attached to the carrier;
the active component is composed of one or more of metals Rh, Pt, Pd, Ir, Au, Ag, Ni and Re (called other active metals) and a noble metal Ru, preferably, the active component is a bimetallic or trimetal system composed of Au and/or Ni and Ru;
the content of the active component Ru is 0.005-20% of the mass of the carrier, preferably 0.01-10%, more preferably 0.1-5%; the content of other active metals is 0.0005-10%, preferably 0.01-5%, more preferably 0.1-1% of the mass of the carrier;
preferably, in the active component, the mass ratio of the other active metal to the metal Ru is 0.001: 1-10: 1, and more preferably 0.03: 1-1: 1.
The auxiliary agent consists of an auxiliary agent I and an auxiliary agent II, wherein the auxiliary agent I consists of metal Eu and metal Yb, and the auxiliary agent II is selected from one or more of metal Li, Na, K, Cu, Co, Fe, Zn, Mn, La and Ce, preferably one or more of Mn, Zn and La.
The content of the first auxiliary agent is 0.001-0.5 percent of the mass of the carrier, and preferably 0.01-0.1 percent; the Eu/Yb mass ratio in the first auxiliary agent is 0.01: 1-100: 1, preferably 0.01-1: 1;
the content of the second auxiliary agent is 0.001-0.5 percent of the mass of the carrier, and preferably 0.01-0.1 percent;
preferably, the mass ratio of the first auxiliary agent to the second auxiliary agent is 0.05: 1-1000: 1, preferably 0.5: 1-100: 1;
preferably, in the catalyst, the mass ratio of the auxiliary agent to the active component is 0.0001: 1-0.2: 1, and more preferably 0.005: 1-0.1: 1.
The carrier is a molecular sieve modified by a metal compound, the molecular sieve is one or more of SBA-15 molecular sieve, Y-type molecular sieve, beta molecular sieve, MCM-22, MCM-41, MCM-48, MCM-49, ZSM-5, ZSM-35 and ZSM-50, and preferably one or more of SBA-15 molecular sieve, beta molecular sieve and MCM-41;
the metal compound comprises one or more of metal oxide, metal hydroxide and metal carbonate, preferably CaO, MgO, BaO and V 2 O 5 、Cr 2 O 3 、WO 2 、WO 3 、MoO 2 、MoO 3 、Ca(OH) 2 、Mg(OH) 2 、CaCO 3 、BaCO 3 、SrCO 3 More preferably CaO, Mg (OH) 2 、BaCO 3 One or more of;
the mass ratio of the metal compound to the molecular sieve in the carrier is 0.001: 1-1: 1, preferably 0.01: 1-0.2: 1.
In the catalyst, the metal compound effectively regulates the strength, total acid amount and crystal microstructure of the molecular sieve acid, inhibits the catalytic action of the carrier on the m-xylylenediamine hydrogenation side reaction, and improves the product selectivity. The other active metals and the active metal Ru form an alloy, so that the adsorption and activation capacity of the catalyst on hydrogen can be obviously improved, and the hydrogenation reaction can be quickly carried out under lower hydrogen pressure. The first auxiliary agent is highly dispersed on the surface of the carrier, so that the dispersion and anchoring of active components (Ru and other active metals) are facilitated; the two pairs of auxiliary agents carry out effective electronic and structural modulation on the surfaces of active components (Ru and other active metals), and the first auxiliary agent and the second auxiliary agent have synergistic effect, so that the activity, the selectivity and the service life of the catalyst are improved.
In another aspect of the present invention, there is also provided a method for preparing the above catalyst, which comprises:
(1) preparing a metal compound modified molecular sieve: weighing a certain amount of a metal compound precursor for modifying a molecular sieve, adding water to dissolve the metal compound precursor, adding a certain mass of the molecular sieve, heating to 30-80 ℃, adding a certain mass of sodium hydroxide and/or sodium carbonate, stirring for 2-10 h, cooling to room temperature, filtering, washing, drying at 80-120 ℃, then placing in a muffle furnace, roasting at a certain temperature for a period of time, and then cooling to room temperature for later use;
(2) loading of an auxiliary agent: weighing a certain mass of the modified molecular sieve carrier obtained in the step (1) and auxiliary agents, namely metal Eu and Yb, adding the modified molecular sieve carrier and the auxiliary agents into an autoclave, replacing the modified molecular sieve carrier and the auxiliary agents with nitrogen, exhausting air in the autoclave, adding a certain mass of liquid ammonia, stirring for a period of time at a certain temperature, then heating/cooling to room temperature, exhausting nitrogen and liquid ammonia in the autoclave, opening the autoclave, flushing a catalyst in the autoclave with ethanol, filtering, washing with ethanol and distilled water respectively, drying at 80-120 ℃, then placing the autoclave in a muffle furnace, roasting at a certain temperature for a period of time under an inert gas atmosphere, and then cooling to room temperature for later use;
(3) and (3) loading an active component and an auxiliary agent II: weighing a certain mass of ruthenium salt (preferably RuCl) 3 .3H 2 O), other active metal precursors and an auxiliary agent secondary precursor to prepare an aqueous solution A; weighing a certain mass of surfactant, and dissolving the surfactant with alcohol to prepare a solution B;
and (3) adding the solution B into the solution A, stirring, controlling a certain constant temperature, adding a certain amount of reducing boride aqueous solution, adding the carrier treated in the step (2) into the system, stirring for a period of time, filtering, washing with ethanol, acetone and water respectively, drying in a nitrogen atmosphere, cooling to room temperature, extruding into strips and forming to obtain the small columnar catalyst with the diameter of 0.5-5 mm and the length of 1-5 mm.
(4) Activating the catalyst: the catalyst needs to be activated before use, and the activation method comprises the following steps: and (3) placing the catalyst formed in the step (3) into a reaction tube, continuously introducing hydrogen, heating to a certain temperature, introducing a certain amount of organic micromolecule amine compound at a certain speed, and cooling to room temperature to obtain the activated catalyst.
In the preparation method of the catalyst, in the step (1), the precursor of the metal compound for modifying the molecular sieve is soluble salt of corresponding metal, such as one or more of metal nitrate, sulfate and chloride, preferably metal nitrate;
in the preparation method of the catalyst, in the step (1), the molar ratio of sodium hydroxide and/or sodium carbonate to the metal compound precursor is 1-20, preferably 4-10;
in the preparation method of the catalyst, the roasting temperature in the step (1) is 100-700 ℃, and preferably 200-500 ℃; the roasting time is 1-20 h, preferably 4-10 h;
in the preparation method of the catalyst, in the step (2), the mass ratio of liquid ammonia/(carrier + auxiliary agent-metal) is 0.5-20, preferably 2-10;
in the preparation method of the catalyst, in the step (2), after liquid ammonia is added, the temperature of the system is controlled to be-40 ℃, and is preferably-10-20 ℃; the stirring time is 1-20 h, preferably 5-10 h under the temperature condition;
in the preparation method of the catalyst, the roasting temperature in the step (2) is 200-800 ℃, and preferably 400-600 ℃;
in the preparation method of the catalyst, the roasting time in the step (2) is 1-20 hours, preferably 5-10 hours.
In the preparation method of the catalyst, in the step (3), in the pre-solution a, the amount of water used is not particularly limited, and the components may be completely dissolved, for example, water and (RuCl) 3 .3H 2 O + other active metal precursor + auxiliary agent secondary precursor) in a mass ratio of 5-1000, preferably 20-200;
in the preparation method of the catalyst, in the step (3), the surfactant is one or more of PEG-400, PEG-600, PEG-6000, PEG-10000, PEG-20000, PVP, PVA, CTAB, nonylphenol polyoxyethylene ether, oleic acid, palmitic acid, oleylamine and the like, and preferably one or more of PEG-600, CTAB and PVP;
in the preparation method of the catalyst, in the step (3), the alcohol used for preparing the solution B is one or more of ethanol, propanol, 1, 2-propylene glycol, glycerol, diethylene glycol, glycerol, PPG and cyclohexanol, and preferably one or more of glycerol and glycerol;
in the preparation method of the catalyst, in the step (3), the mass ratio of the alcohol to the surfactant in the solution B is 10-2000, preferably 50-200;
in the preparation method of the catalyst, in the step (3), the mass ratio of the surfactant to the metal salt (ruthenium salt + other active metal precursor + auxiliary agent bipolymer) is 1-1000, preferably 20-100;
in the preparation method of the catalyst, in the step (3), the solution B is added into the solution A and uniformly stirred, and the temperature of the system is controlled to be 10-70 ℃, preferably 20-40 ℃;
in the preparation method of the catalyst, in the step (3), the volume molar concentration of the reductive boride aqueous solution is 0.2-3.0 mol/L; the reducing boride is selected from NaBH 4 、KBH 4 、LiBH 4 And ammonia borane, preferably NaBH 4 And/or KBH 4 The molar ratio of the reducing boride to the active component metal salt (ruthenium salt + other active metal precursors) is 5-20, preferably 8-12.
In the preparation method of the catalyst, after the carrier treated in the step (2) is added in the step (3), stirring is carried out for 1-10 hours, preferably 2-4 hours;
in the preparation method of the catalyst, the hydrogen introduction rate in the step (4) is 20-1000 mL/g Catalyst and process for preparing same Preferably 100 to 500mL/g Catalyst and process for preparing same /h；
In the preparation method of the catalyst, in the step (4), the temperature is raised to 200-500 ℃, and preferably 250-350 ℃;
in the preparation method of the catalyst, the organic small molecular amine in the step (4) is one or more of methylamine, ethylamine, ethylenediamine, diethylamine, propylamine, propylenediamine, butylamine and butylenediamine, preferably methylamine and ethylenediamine;
in the preparation method of the catalyst, in the step (4), the ratio of the total mass of the introduced small molecular amine compounds to the mass of the catalyst is 10-200, preferably 50-100; the speed of introducing the micromolecule amine compound is 5-100 g/g based on the mass airspeed of the micromolecule amine compound Catalyst and process for preparing same Preferably 20 to 60g/g Catalyst and process for preparing same /h。
In another aspect, the invention relates to the application of the catalyst in catalyzing the hydrogenation of m-xylylenediamine to synthesize 1, 3-cyclohexyldimethylamine: in a preferred embodiment, the method comprises the following steps: in a fixed bed reactor, m-xylylenediamine is used as a hydrogenation substrate, the reaction solvent is one or more selected from alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, cyclohexanol, cyclohexanediol, etc., ether solvents such as tetrahydrofuran, dioxane, dimethyl ether, diethyl ether, etc., cycloalkane solvents such as cyclohexane, methylcyclohexane, 1, 2-dimethylcyclohexane, 1, 3-dimethylcyclohexane, 1, 4-dimethylcyclohexane, decalin, etc., and amine solvents such as 1, 3-cyclohexyldimethylamine, cyclohexylamine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanediamine, etc., preferably tetrahydrofuran and/or isopropanol; the mass concentration of the substrate is 10-80%, preferably 30-60%; the reaction temperature is 40-120 ℃, and preferably 60-90 ℃; the reaction pressure is 2-9 MPa, preferably 4-7 MPa; the reaction space velocity is 0.1-2 in terms of the hourly feeding mass of m-xylylenediamine/the mass of the catalyst.0h -1 Preferably 0.3 to 1.0 hour -1 ，H 2 The mol ratio of m-xylylenediamine/m-xylylenediamine is 5 to 100, preferably 10 to 30.
The invention has the beneficial effects that:
dissolving an assistant metal in liquid ammonia to form a metal amide, uniformly adsorbing the metal amide by a carrier, decomposing the metal amide to form metal imine or nitride through drying and roasting, highly dispersing the metal imine or nitride on the carrier, and modifying the surface of the carrier, so that the adsorption, dispersion and anchoring of the carrier to active components are facilitated; the second auxiliary agent can carry out effective electronic and structural modulation on the surface of the active component, and the first auxiliary agent and the second auxiliary agent have synergistic effect, so that the activity, the selectivity and the service life of the catalyst are improved; other active metals and metal Ru form alloy, which obviously improves the adsorption and activation capability of the catalyst on hydrogen, and ensures that the hydrogenation reaction can be rapidly carried out under lower hydrogen pressure. Under the condition of hydrogen introduction, the catalyst is subjected to high-temperature treatment by utilizing the organic micromolecule amine, so that the carrier and the active surface can be further modified, and the selectivity and the stability of the catalyst are improved. The catalyst is used for catalyzing the hydrogenation reaction of m-xylylenediamine, the conversion rate of raw materials can reach more than 99 percent, and the selectivity of products can reach more than 98 percent under the conditions of lower reaction temperature and pressure, higher substrate concentration and reaction space velocity. The catalyst of the present invention has stable activity and selectivity and long service life after long-term continuous operation. The catalyst of the invention is simple to prepare and easy to industrialize.
Detailed Description
The invention is further illustrated by the following examples, but is not limited to the examples set forth. The conditions for gas chromatography in the following examples were: an Agilent HP-INNOWAX chromatographic column, wherein the injection port temperature is 240 ℃, the temperature of an FID detector is 250 ℃, the flow rate of the column is 1.2mL/min, the hydrogen flow rate is 40mL/min, the air flow rate is 400mL/min, the temperature programming mode is that the temperature is kept for 2min at 50 ℃, the temperature is increased to 80 ℃ at 5 ℃/min, then the temperature is increased to 240 ℃ at 15 ℃/min, and the temperature is kept for 10 min.
Example 1
(1) Weighing 20g Ca (NO) 3 ) 2 .4H 2 O, dissolving in 200g of water, addingAdding 150g of SBA-15 molecular sieve, heating to 50 ℃, adding 5g of NaOH, stirring for 5h, filtering, washing with distilled water until the pH value is 7, drying a filter cake at 100 ℃ for 10h, roasting at 400 ℃ for 6h, and cooling to room temperature for later use;
(2) weighing 100g of the modified molecular sieve obtained in the step (1), 0.005g of metal Eu and 0.05g of Yb, adding the modified molecular sieve, the metal Eu and the 0.05g of Yb into a 1L high-pressure kettle, filling 1MPa of nitrogen for replacement, repeating the replacement for 3 times, adding 200g of liquid ammonia, heating the mixture in a water bath to 40 ℃, stirring the mixture for 5h, then cooling the mixture to room temperature, exhausting the nitrogen and the liquid ammonia in the kettle, opening the kettle, flushing the catalyst in the kettle with ethanol, filtering out a carrier, washing the carrier with ethanol and distilled water respectively, and drying the carrier at 110 ℃; placing the dried carrier in a muffle furnace, roasting for 5 hours at 500 ℃ in a nitrogen atmosphere, and then cooling to room temperature for later use;
(3) 1.02g of RuCl was weighed out separately 3 .3H 2 O with 0.21g H [ AuCl ] 4 ]And 0.20g Mn (NO) 3 ) 2 .4H 2 Dissolving O in 50g of distilled water, and uniformly stirring to obtain a solution A; then weighing 30g of PEG-600 surfactant, and dissolving with 1500g of glycerol to obtain a solution B; adding the solution B into the solution A, quickly stirring, heating to 40 ℃, and dropwise adding 1mol/L NaBH at the speed of 25mL/min 4 After the water solution is added, continuously stirring for 1h, weighing 50g of the carrier obtained in the step (2), adding the carrier into the system, stirring for 5h, filtering, washing with ethanol, acetone and water respectively, drying at 100 ℃ for 4h under the protection of nitrogen, and cooling to room temperature; extruding and molding to obtain a small cylindrical catalyst with the diameter of 2mm and the length of 3 mm;
(4) and (3) placing the catalyst obtained in the step (3) in a reaction tube, continuously introducing hydrogen at the rate of 5000mL/h, heating to 300 ℃, introducing 5000g of methylamine at the rate of 2000g/h, and cooling to room temperature to obtain the required catalyst, wherein the catalyst is marked as C1.
Example 2
A catalyst sample C2 was prepared by the same procedure as in example 1, except that in step (3), 40g CTAB was added instead of PEG-600.
Example 3
Catalyst sample C3 was prepared using the same method steps as in example 1, exceptThe method comprises the following steps: step (1) uses 15g Mg (NO) 3 ) 2 .6H 2 O instead of 20g Ca (NO) 3 ) 2 .4H 2 O, replacement of SBA-15 by 100g of beta molecular sieves, RuCl in step (3) 3 .3H 2 O mass 5.10g, H [ AuCl ] 4 ]The mass is 0.11g, NaBH with the concentration of 1mol/L is dripped at the speed of 50mL/min 4 200mL of the aqueous solution was introduced, and 4000g of ethylenediamine was introduced at a rate of 1000g/h instead of methylamine in step (4).
Example 4
Catalyst sample C4 was prepared using the same process steps as example 1, except: in the step (2), Eu is 0.001g, Yb is 0.10g, and in the step (3), Ni (NO) is added in an amount of 0.42g 3 ) 2 .6H 2 O。
Example 5
Catalyst sample C5 was prepared by the same procedure as in example 1, except that 10g of Ba (NO) was used in step (1) 3 ) 2 Substitute for 20g Ca (NO) 3 ) 2 .4H 2 O, over 10g of Na 2 CO 3 Instead of 5g NaOH; 400g of liquid ammonia is added in the step (2), and 10g of PVP is dissolved in 1000g of glycerol to prepare a solution B in the step (3).
Example 6
Catalyst sample C6 was prepared using the same method steps as in example 1, except that the calcination temperature in step (2) was 300 ℃ and RuCl in step (3) 3 .3H 2 O was 0.51 g.
Example 7
Catalyst sample C7 was prepared using the same process steps as in example 1, except that in step (1) MCM-41 of the same mass was used in place of SBA-15; in step (3), 0.10g of La (NO) was added 3 ) 3 .6H 2 O instead of 0.20g Mn (NO) 3 ) 2 .4H 2 O; step (4) 3000g of ethylenediamine was continuously introduced at a rate of 500g/h, instead of methylamine.
Example 8
Catalyst sample C8 was prepared using the same process steps as in example 1, except that 0.25g Zn (NO) was used in step (3) 3 ) 2 .6H 2 O instead of 0.20g Mn (NO) 3 ) 2 .4H 2 O, step (4) 10000g of propylamine were continuously fed in at a rate of 2500g/h instead of methylamine.
Comparative example 1
Catalyst sample D1 was prepared using the same method steps as example 1, except that no H [ AuCl ] was added in step (3) 4 ]。
Comparative example 2
Catalyst sample D2 was prepared using the same process steps as in example 1, except that Eu and Yb were not added in step (2).
Comparative example 3
Catalyst sample D3 was prepared using the same process steps as in example 1, except that Eu was not added in step (2).
Comparative example 4
Catalyst sample D4 was prepared by the same procedure as in example 1, except that methylamine was not charged after the heating in step (4) to 300 ℃ and held at that temperature for 5 hours, and then cooled to room temperature in this continuously charged state to obtain catalyst D4.
Comparative example 5
Catalyst sample D5 was prepared using the same process steps as in example 1, except that Mn (NO) was not added in step (3) 3 ) 2 .4H 2 O。
Comparative example 6
Catalyst sample D6 was prepared using the same process steps as in example 1, except that step (1) was omitted and 100g of SBA-15 catalyst was added directly to step (2).
Example 1A
50g of catalyst is weighed and filled in a reaction tube with the length of 150cm, the inner diameter of 24mm and the outer diameter of 40mm, and a certain amount of quartz sand is filled at each end of the reaction tube. The reaction device is respectively replaced by nitrogen and hydrogen, air is exhausted, then hydrogen is introduced to 5MPa, and the hydrogen flow is set to be 90L/H (H) 2 The mol ratio of m-xylylenediamine/m-xylylenediamine is 18.2), continuously introducing hydrogen, heating to 70 ℃ at the heating rate of 120 ℃/h, keeping the temperature, and introducing a THF solution of m-xylylenediamine (the mass concentration of m-xylylenediamine in the solution is 5) into the reactor at the speed of 1g/min by using a high-pressure constant-flow pump0%) and the hydrogenation reaction was continuously carried out under the stable conditions, and after 200h, sampling was carried out and quantitative analysis was carried out by gas chromatography. The reaction results are shown in Table 1.
Examples 2A to 8A
The same hydrogenation procedure as in example 1A was used, except that the catalysts 2A to 8A corresponded to C2 to C8, respectively. The reaction results are shown in Table 1.
Example 9A
The same hydrogenation reaction procedure as in example 1A was used, except that the hydrogenation reaction solvent was isopropanol, the reaction temperature was 90 ℃ and the reaction pressure was 7 MPa.
Example 10A
The same hydrogenation reaction procedure as in example 1A was conducted except that the concentration of the hydrogenation substrate was 20% by mass, the feeding rate of the solution of m-xylylenediamine in THF was 0.83g/min, and the space velocity was 0.2h -1 ) The hydrogen flow rate was 45L/h.
Example 11A
The same hydrogenation reaction procedure as in example 1A was employed except that the concentration of the hydrogenation substrate was 70% by mass, the feeding rate of the THF solution of m-xylylenediamine was 0.71g/min, the reaction temperature was 60 ℃ and the reaction pressure was 9 MPa. .
Comparative examples 1A to 6A
The same hydrogenation procedure as in example 1A was employed except that 50g of each of the D1-D6 catalysts was charged into the reactor, and the reaction results are shown in Table 1.
Comparative example 7A
The same hydrogenation procedure as in example 1A was used, except that the reactor was charged with 50g of commercially available Ru/Al at 2% loading 2 O 3 Catalyst (marked as D7), reaction solvent is liquid ammonia, mass concentration of substrate is 15%, and reaction space velocity is 0.2h -1 The reaction temperature was 100 ℃ and the pressure was 10MPa, and the reaction results are shown in Table 1.
Table 1:
example 1B
The same hydrogenation procedure as in example 1A was used and a life test of the C1 catalyst was carried out. The reaction results are shown in Table 2.
Comparative example 1B
The same hydrogenation procedure as in comparative example 7A was used and a life test of the D7 catalyst was performed. The reaction results are shown in Table 2.
Table 2:
from the above table data, it can be seen that the catalyst of the present invention has excellent activity and selectivity, and can catalyze the hydrogenation of m-xylylenediamine to prepare 1, 3-cyclohexyldimethylamine with high selectivity at lower reaction temperature and pressure by using conventional alcohol or ether solvents, and particularly, the catalyst of the present invention has stable activity and selectivity and long service life.
Claims (21)
1. The catalyst for synthesizing the 1, 3-cyclohexyldimethylamine by hydrogenating the m-xylylenediamine is characterized by comprising a carrier, and an active component and an auxiliary agent which are attached to the carrier;
the active component is composed of one or more of metals Rh, Pt, Pd, Ir, Au, Ag, Ni and Re and a noble metal Ru, wherein one or more of the metals Rh, Pt, Pd, Ir, Au, Ag, Ni and Re is called as other active metals;
the auxiliary agent consists of an auxiliary agent I and an auxiliary agent II, wherein the auxiliary agent I consists of metal Eu and metal Yb, and the auxiliary agent II is selected from one or more of metal Li, Na, K, Cu, Co, Fe, Zn, Mn, La and Ce;
the preparation method of the catalyst comprises the following steps:
(1) loading of an auxiliary agent: weighing a certain mass of carrier, metal Eu and Yb, adding the carrier, the metal Eu and the metal Yb into a high-pressure kettle, adding a certain mass of liquid ammonia, controlling a certain temperature, stirring for a period of time, filtering, washing, drying and roasting;
(2) and (3) loading an active component and an auxiliary agent II: weighing ruthenium salt, other active metal precursors and an auxiliary agent secondary precursor according to a certain mass to prepare a water solution A; weighing a certain mass of surfactant, and dissolving the surfactant with alcohol to prepare a solution B;
and (2) mixing the solution B with the solution A, adding a certain amount of reducing boride aqueous solution, adding the carrier treated in the step (1) into the system, stirring for a period of time, filtering, washing, drying, extruding into strips and forming to obtain the catalyst.
2. The catalyst according to claim 1, characterized in that the active component is a bimetallic or trimetallic system of Au and/or Ni and Ru; the second auxiliary agent is selected from one or more of Mn, Zn and La.
3. The catalyst according to claim 1, wherein the content of Ru is 0.005-20% of the mass of the carrier; the content of other active metals is 0.0005-10% of the mass of the carrier.
4. The catalyst according to claim 1, wherein the content of Ru is 0.01-10% of the mass of the carrier; the content of other active metals is 0.01-5% of the mass of the carrier.
5. The catalyst according to claim 1, wherein the content of Ru is 0.1-5% of the mass of the carrier; the content of other active metals is 0.1-1% of the mass of the carrier.
6. The catalyst according to any one of claims 1 to 5, wherein the content of the first auxiliary agent is 0.001 to 0.5 percent of the mass of the carrier; the Eu/Yb mass ratio in the auxiliary agent I is 0.01: 1-100: 1;
the content of the second auxiliary agent is 0.001-0.5% of the mass of the carrier.
7. The catalyst according to claim 6, wherein the content of the first auxiliary agent is 0.01-0.1% of the mass of the carrier; the mass ratio of Eu to Yb in the first auxiliary agent is 0.01-1: 1;
the content of the second auxiliary agent is 0.01-0.1% of the mass of the carrier.
8. The catalyst according to any one of claims 1 to 5 and 7, wherein the carrier is a molecular sieve modified by a metal compound, and the molecular sieve is one or more of an SBA-15 molecular sieve, a Y-type molecular sieve, a beta molecular sieve, MCM-22, MCM-41, MCM-48, MCM-49, ZSM-5, ZSM-35 and ZSM-50;
the metal compound comprises one or more of metal oxide, metal hydroxide and metal carbonate;
the mass ratio of the metal compound to the molecular sieve in the carrier is 0.001: 1-1: 1.
9. The catalyst of claim 8, wherein the molecular sieve is one or more of SBA-15 molecular sieve, beta molecular sieve, MCM-41;
the metal compound is selected from CaO, MgO, BaO and V 2 O 5 、Cr 2 O 3 、WO 2 、WO 3 、MoO 2 、MoO 3 、Ca(OH) 2 、Mg(OH) 2 、CaCO 3 、BaCO 3 、SrCO 3 One or more of;
the mass ratio of the metal compound to the molecular sieve in the carrier is 0.01: 1-0.2: 1.
10. Catalyst according to claim 9, characterized in that the metal compound is selected from CaO, Mg (OH) 2 、BaCO 3 One or more of (a).
11. The catalyst according to claim 8, wherein the preparation method of the carrier comprises: dissolving a metal compound precursor in water, adding a molecular sieve, heating to 30-80 ℃, adding a certain mass of sodium hydroxide and/or sodium carbonate, filtering, washing, drying and roasting to obtain a carrier;
the metal compound precursor is soluble salt of corresponding metal, including one or more of nitrate, sulfate and chloride; the molar ratio of the sodium hydroxide and/or the sodium carbonate to the metal compound precursor is 1-20; the roasting temperature is 100-700 ℃; the roasting time is 1-20 h.
12. The catalyst according to claim 11, wherein the metal compound precursor is a nitrate of the corresponding metal; the molar ratio of the sodium hydroxide and/or the sodium carbonate to the metal compound precursor is 4-10; the roasting temperature is 200-500 ℃; the roasting time is 4-10 h.
13. The catalyst according to claim 1, wherein in the step (1), the mass ratio of liquid ammonia/(carrier + Eu + Yb) is 0.5 to 20; after adding liquid ammonia, controlling the temperature of the system to be-40 ℃, and stirring for 1-20 h; the roasting temperature is 200-800 ℃; the roasting time is 1-20 h.
14. The catalyst according to claim 13, wherein in the step (1), the mass ratio of liquid ammonia/(carrier + Eu + Yb) is 2 to 10; after adding liquid ammonia, controlling the temperature of the system to be-10-20 ℃, and stirring for 5-10 h; the roasting temperature is 400-600 ℃; the roasting time is 5-10 h.
15. The catalyst according to claim 1, wherein in the step (2), the surfactant is one or more selected from the group consisting of PEG-400, PEG-600, PEG-6000, PEG-10000, PEG-20000, PVP, PVA, CTAB, nonylphenol polyoxyethylene ether, oleic acid, palmitic acid, oleylamine, and the like;
the alcohol for preparing the solution B is one or more of ethanol, propanol, 1, 2-propylene glycol, glycerol, PPG and cyclohexanol;
the mass ratio of the alcohol to the surfactant in the solution B is 10-2000;
the reducing boride is selected from NaBH 4 、KBH 4 、LiBH 4 And one or more of ammonia borane, wherein the molar ratio of the reductive boride to the active component metal salt is 5-20.
16. The catalyst according to claim 15, wherein in step (2), the surfactant is one or more of PEG-600, CTAB, PVP;
the alcohol for preparing the solution B is one or more of glycerol and glycerol;
the mass ratio of the alcohol to the surfactant in the solution B is 50-200;
the reducing boride is selected from NaBH 4 And/or KBH 4 The molar ratio of the reducing boride to the active component metal salt is 8-12.
17. The catalyst according to any one of claims 1 and 13 to 16, further comprising a step of activating the prepared catalyst, which comprises placing the catalyst formed in the step (2) in a reaction tube, continuously introducing hydrogen, heating to a certain temperature, introducing a certain amount of organic small molecular amine compound at a certain rate, and then cooling to room temperature to obtain the activated catalyst;
wherein the hydrogen introduction rate is 20-1000 mL/g Catalyst and process for preparing same H; the ratio of the total mass of the introduced small molecular amine compounds to the mass of the catalyst is 10-200; the speed of introducing the small molecular amine compound is 5-100 g/g Catalyst and process for preparing same /h。
18. The catalyst according to claim 17, wherein the hydrogen introduction rate is 100 to 500mL/g Catalyst and process for preparing same H; the ratio of the total mass of the introduced small molecular amine compounds to the mass of the catalyst is 50-100; the speed of introducing the small molecular amine compound is 20-60 g/g Catalyst and process for preparing same /h。
19. Use of the catalyst according to any one of claims 1 to 18 for catalyzing the hydrogenation of m-xylylenediamine to 1, 3-cyclohexyldimethylamine.
20. The use according to claim 19, wherein the mass concentration of m-xylylenediamine is 10 to 80%(ii) a The reaction pressure is 2-9 MPa; the reaction temperature is 40-120 ℃; the feeding airspeed of the m-xylylenediamine is 0.1-2.0 h -1 。
21. The use according to claim 19, wherein the mass concentration of m-xylylenediamine is 30-60%; the reaction pressure is 4-7 MPa; the reaction temperature is 60-90 ℃; the feeding airspeed of the m-xylylenediamine is 0.3-1.0 h -1 。
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| CN112047843B (en) * | 2020-09-04 | 2023-01-17 | 万华化学集团股份有限公司 | Method for improving stability of m-xylylenediamine fixed bed hydrogenation catalyst |
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| CN115739104A (en) * | 2022-11-30 | 2023-03-07 | 山东海科创新研究院有限公司 | M-xylylenediamine catalyst, and preparation method and application thereof |
| CN116273145A (en) * | 2023-03-30 | 2023-06-23 | 华能景泰热电有限公司 | Application method of supported iron-based catalyst in integrated removal of flue gas of coal-fired power plant |
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