CN110773175A - Supported metal catalyst, preparation method and application thereof, and synthesis process of N-methylmorpholine - Google Patents
Supported metal catalyst, preparation method and application thereof, and synthesis process of N-methylmorpholine Download PDFInfo
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- CN110773175A CN110773175A CN201911082115.9A CN201911082115A CN110773175A CN 110773175 A CN110773175 A CN 110773175A CN 201911082115 A CN201911082115 A CN 201911082115A CN 110773175 A CN110773175 A CN 110773175A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
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Abstract
The invention relates to the technical field of organic synthesis, in particular to a supported metal catalyst, a preparation method and application thereof and a synthesis process of N-methylmorpholine. The supported metal catalyst comprises Al
2O
3‑TiO
2Carrier and Al supported on the carrier
2O
3‑TiO
2Active metal of a carrier, wherein the mass of the active metal accounts for 15-30% of the mass of the supported metal catalyst. The catalyst has good stability, good activity and good catalytic effect, and ensures that the conversion rate of the morpholine raw material is high and the synthesis yield of the N-methylmorpholine is high.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a supported metal catalyst, a preparation method and application thereof and a synthesis process of N-methylmorpholine.
Background
N-methylmorpholine is a colorless and transparent heterocyclic tertiary amine with ammonia smell, is an important fine chemical raw material and organic solvent, is mainly used as a polyurethane catalyst, a solvent, an extracting agent and a rubber accelerator, and is also an important intermediate for synthesizing pesticides, medicines and surfactants.
The method for preparing N-methylmorpholine has more reports in documents, and the method mainly comprises the following steps according to the used raw material classification: a cyclization method by an N-methyldiethanolamine method; a methyl cyclization method such as a diglycolamine method or a dimethyl sulfate method; a methylation method of morpholine, formaldehyde and formic acid; morpholine and chloromethane methylation method. These methods are all batch processes, and have expensive raw materials, low production efficiency and high cost. At present, the simplest method for producing N-methylmorpholine is to take morpholine and methanol as raw materials to carry out methylation reaction.
However, even if the reaction process of morpholine and methanol is improved, the yield and purity of the reaction still cannot be improved well.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a supported metal catalyst, a preparation method and application thereof and a synthesis process of N-methylmorpholine.
The inventor finds that the catalyst adopted in the reaction process of morpholine and methanol has great influence on the yield and purity of the catalyst, and the catalyst used in the prior art has many disadvantages, such as high metal content, high preparation process of the catalyst, easy loss of metal, influence on the activity and service life of the catalyst, poor catalytic effect, and low yield and product purity of N-methylmorpholine. Therefore, the catalyst provided by the invention has the advantages of good stability, good activity and good catalytic effect, and ensures that the synthesis yield and the purity of the N-methylmorpholine are high.
The invention is realized by the following steps:
in a first aspect, embodiments provide a supported metal catalyst comprising Al
2O
3-TiO
2Carrier and Al supported on the carrier
2O
3-TiO
2Active metal of a carrier, wherein the mass of the active metal accounts for 15-30% of the mass of the supported metal catalyst.
In alternative embodiments, the active metal comprises at least two of Ni, Cu, Co, Zn and La;
preferably, the active metal includes at least Cu and Ni;
preferably, the active metals include Ni, Cu, and Co;
preferably, the active metal includes Ni, Cu, and La.
In an alternative embodiment, when the active metal comprises Cu, the mass of Cu is 10-20% of the mass of the supported metal catalyst;
preferably, when the active metal comprises Ni, the mass of Ni accounts for 5-10% of the mass of the supported metal catalyst;
preferably, the mass of Zn accounts for 0-10% of the mass of the supported metal catalyst;
preferably, the mass of Co accounts for 0-5% of the mass of the supported metal catalyst;
preferably, the mass of La accounts for 0-0.2% of the mass of the supported metal catalyst.
In an alternative embodiment, the Al
2O
3-TiO
2The shape of the carrier is any one of a cylinder, a hollow cylinder, a sphere, a clover and a clover; preferred are clover type and hollow cylinder type.
In a second aspect, embodiments provide a method of making a supported metal catalyst as described in any of the preceding embodiments, comprising: in Al
2O
3-TiO
2The carrier is loaded with active metal.
In an alternative embodiment, a secondary impregnation process is used to impregnate the Al
2O
3-TiO
2Supporting the active metal on a carrier;
preferably, the secondary impregnation method comprises impregnating the Al
2O
3-TiO
2The carrier is immersed in a salt solution containing active metals for the first immersion, and then the first drying and the first roasting are carried out; then adding the Al
2O
3-TiO
2The carrier is soaked in a salt solution containing active metal for the second soaking, and then the second drying and the second roasting are carried out;
preferably, the salt solution containing the active metal is a nitrate solution;
preferably, the mass concentration of the nitrate solution is 10-40%;
preferably, the nitrate solution is Ni (NO)
3)
2、Cu(NO
3)
2、Co(NO
3)
2、Zn(NO
3)
2And La (NO)
3)
3A mixed solution of at least two of (1);
preferably, the time of the first impregnation is 6 to 8 hours, and the conditions of the first drying are as follows: 110 ℃ and 130 ℃ for 11-13 hours; the conditions of the first roasting are as follows: 400-550 ℃ for 3.0-5.0 hours;
preferably, the time of the second impregnation is 6 to 8 hours, and the conditions of the second drying are as follows: 110 ℃ and 130 ℃ for 11-13 hours; the conditions of the second roasting are as follows: 400-550 ℃ for 3.0-5.0 hours.
In a third aspect, the examples provide the use of a supported metal catalyst as described in any of the preceding embodiments or as prepared by the method of making a supported metal catalyst as described in the preceding embodiments in the catalytic synthesis of N-methylmorpholine.
In a fourth aspect, an embodiment provides a process for synthesizing N-methylmorpholine, including: the supported metal catalyst prepared by the supported metal catalyst of any of the preceding embodiments or the method of preparing the supported metal catalyst of the preceding embodiments is subjected to a catalytic reaction to form the N-methylmorpholine.
In an alternative embodiment, the catalytic reaction comprises: under the atmosphere of reducing gas, the supported metal catalyst is used for catalyzing morpholine and methanol to carry out gas-solid phase reaction;
preferably, the molar ratio of morpholine to methanol is 1: 1-6;
preferably, the flow rate of the hydrogen is 60-80 ml/min;
preferably, the conditions under which the gas-solid reaction is carried out are: the pressure is 0.6-1.2MPa, and the temperature is 150-;
preferably, after the reaction is finished, post-treatment is carried out;
preferably, the post-treatment comprises the steps of sequentially carrying out gas-liquid separation after the reaction is finished to form a liquid product, then removing methanol and water, and then rectifying to form the N-methylmorpholine;
preferably, the reducing gas is hydrogen.
In an alternative embodiment, before carrying out the gas-solid phase reaction, the method further comprises the step of activating and reducing the supported metal catalyst;
preferably, the activation reduction of the supported metal catalyst comprises: adding the supported metal catalyst into a fixed bed, replacing air in the fixed bed by using inert gas, increasing the temperature to 160-;
preferably, the total activation reduction time is 10-12 hours.
The invention has the following beneficial effects: the supported metal catalyst of the invention uses Al
2O
3-TiO
2The carrier is used, and the amount of the loaded active metal is controlled, so that the loaded metal catalyst has better stability, reaction activity and selectivity, and can catalyze the reaction of morpholine and methanol well, and improve the yield of N-methylmorpholine and the conversion rate of morpholine raw materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
The embodiment of the invention provides a supported metal catalyst, a preparation method and application thereof and a synthesis process of N-methylmorpholine.
The embodiment of the invention provides a supported metal catalyst which comprises Al
2O
3-TiO
2Carrier and Al supported on the carrier
2O
3-TiO
2Active metal of a carrier, wherein the mass of the active metal accounts for 15-30% of the mass of the supported metal catalyst. The supported metal catalyst is prepared from Al
2O
3-TiO
2The carrier is favorable for improving the stability of the supported metal catalyst, the catalytic performance of the supported metal catalyst and the yield of the N-methylmorpholine and the conversion rate of the morpholine raw material. And the loss of metal can be reduced on the basis of ensuring the catalytic performance by further controlling the content of the loaded active metal, so that the performance of the loaded metal catalyst is ensured, and meanwhile, the production cost can be reduced, the difficulty in catalyst preparation is reduced, and the industrial production of the loaded metal catalyst is facilitated.
Further, the active metal includes at least two of Ni, Cu, Co, Zn, and La; preferably, the active metal includes at least Cu and Ni; preferably, the active metals include Ni, Cu, and Co; preferably, the active metal includes Ni, Cu, and La. The specific active metal can ensure the performance of the supported metal catalyst, and particularly the supported metal catalyst contains Co and La, so that the supported metal catalyst has good catalytic performance under the condition of relatively low active metal loading.
Further, when the active metal comprises Cu, the mass of Cu accounts for 10-20% of the mass of the supported metal catalyst, when the active metal comprises Ni, the mass of Ni accounts for 5-10% of the mass of the supported metal catalyst, and preferably, the mass of Zn accounts for 0-10% of the mass of the supported metal catalyst; the mass of Co accounts for 0-5% of the mass of the supported metal catalyst; the mass of La accounts for 0-0.2% of the mass of the supported metal catalyst. The content of each metal in the supported metal catalyst is controlled, so that the stability and the activity of the supported metal catalyst can be more effectively ensured, and meanwhile, the yield of the formed N-methylmorpholine and the conversion rate of the morpholine raw material can be ensured.
Further, Al
2O
3-TiO
2The carrier is in the shape of cylinder, hollow cylinder, sphere,Any one of clover type and clover type; preferred are clover type and hollow cylinder type. The carrier with the properties and the structure can further ensure the catalytic effect of the catalyst.
Further, the embodiment of the invention also provides a preparation method of the supported metal catalyst, which comprises the following steps: in Al
2O
3-TiO
2The carrier is loaded with active metal.
The invention adopts a secondary dipping method to carry out the treatment on the Al
2O
3-TiO
2The active metal is loaded on the carrier, and the secondary impregnation method is adopted to prepare the loaded metal catalyst, so that the influence on the carrier in the preparation process can be reduced, and Al is ensured
2O
3-TiO
2The carrier can well act with active metal, and then the performance of the prepared supported metal catalyst is ensured.
Specifically, the Al is added
2O
3-TiO
2The carrier is immersed in a salt solution containing active metals for the first immersion, and then the first drying and the first roasting are carried out; then adding the Al
2O
3-TiO
2The carrier is impregnated in a salt solution containing the active metal for a second impregnation, followed by a second drying and a second calcination.
Further, the salt solution of the active metal is a nitrate solution; preferably, the mass concentration of the nitrate solution is 10-40%; preferably, the nitrate solution is Ni (NO)
3)
2、Cu(NO
3)
2、Co(NO
3)
2、Zn(NO
3)
2And La (NO)
3)
3At least two of (a) and (b).
Further, the time of the first impregnation is 6-8 hours, and the first drying conditions are as follows: 110 ℃ and 130 ℃ for 11-13 hours; the conditions of the first roasting are as follows: 400-550 ℃ for 3.0-5.0 hours. Preferably, the time of the second impregnation is 6 to 8 hours, and the conditions of the second drying are as follows: 110 ℃ and 130 ℃ for 11-13 hours; the conditions of the second roasting are as follows: 400-550 ℃ for 3.0-5.0 hours.
By adopting the above impregnation process, impregnationThe soaking condition and the salt solution can ensure the smooth reaction and the Al
2O
3-TiO
2The carrier can well load active metal, thereby ensuring the performance of the supported metal catalyst.
Further, the embodiment of the present invention also provides an application of the supported metal catalyst according to any one of the foregoing embodiments or the supported metal catalyst prepared by the preparation method of the supported metal catalyst according to the foregoing embodiments in catalytic synthesis of N-methylmorpholine.
Further, an embodiment of the present invention further provides a synthesis process of N-methylmorpholine, including: the supported metal catalyst prepared by the supported metal catalyst of any of the preceding embodiments or the method of preparing the supported metal catalyst of the preceding embodiments is subjected to a catalytic reaction to form the N-methylmorpholine.
Firstly, the supported metal catalyst is activated and reduced, so that the catalytic effect of the supported metal catalyst is ensured, the reaction is ensured to be carried out smoothly, and the yield of the N-methylmorpholine and the conversion rate of the morpholine raw material are improved.
Specifically, the supported metal catalyst is added into the fixed bed, then the air in the fixed bed is replaced by inert gas, then under the atmosphere of inert gas, the temperature is increased to 160-; preferably, the total activation reduction time is 10-12 hours. The activation reduction is carried out by adopting the temperature and the mode, so that the activation effect of the catalyst is ensured, the adverse effect on the catalyst caused by overhigh temperature is avoided, and the performance of the catalyst is ensured.
It should be noted that the replacement of air allows only inert gas to be present in the reactor and air to be removed; the replacement of the reducing gas is such that only the reducing gas is present in the reactor, while the inert gas is discharged.
And then, under the atmosphere of reducing gas, the supported metal catalyst is used for catalyzing morpholine and methanol to carry out gas-solid reaction.
Wherein the mol ratio of morpholine to methanol is 1: 1-6; preferably, the flow rate of the hydrogen is 60-80 ml/min; the conditions for carrying out the gas-solid reaction are as follows: the pressure is 0.6-1.2MPa, and the temperature is 150-.
The reducing gas is hydrogen, and during the reaction, morpholine and methanol are used as gases, and the space velocity of the mixed gas formed by morpholine and methanol is 0.1-0.3 g/h/ml; that is, the space velocity of the mixed liquid of morpholine and methanol entering the catalyst bed layer in a gaseous state is 0.1-0.3g/h/ml (mass (g) of the catalyst treatment raw material per unit volume (ml) of the hour). The conditions are adopted to ensure the smooth reaction, reduce the occurrence of side reactions and improve the yield of the N-methylmorpholine.
After the reaction is finished, carrying out post-treatment; preferably, the post-treatment comprises the steps of sequentially carrying out gas-liquid separation after the reaction is finished to form a liquid product, then removing methanol and water, and then rectifying to form the N-methylmorpholine.
The whole synthesis process has good process continuity and strong process controllability, is easy to realize industrialization, and can improve the conversion rate of raw materials and the product yield by adopting the catalyst.
Example 1
This example provides a supported metal catalyst comprising Al
2O
3-TiO
2Carrier and carrier supported on Al
2O
3-TiO
2The active metal of the carrier accounts for 24.37 percent of the mass of the supported metal catalyst.
The active metals include Ni, Cu and La. Wherein the mass of Ni accounts for 7.42% of the mass of the supported metal catalyst; the mass of Cu accounted for 16.87% of the mass of the supported metal catalyst, and the mass of La accounted for 0.08% of the mass of the supported metal catalyst.
This embodiment also provides a method for preparing a supported metal catalyst, which comprises:
a) 85.60g of copper nitrate, 48.80g of nickel nitrate and 0.25g of lanthanum nitrate are dissolved in 100ml of distilled water, and the volume of the nitrate aqueous solution is determined to the required concentration for later use; mixing 40g clover type Al
2O
3-TiO
2Soaking the carrier into 100ml of solution for 6 hours, and then draining to obtain filtrate and a catalyst intermediate;
b) drying the catalyst intermediate obtained in the step a) at 120 ℃ for 12 hours, then putting the dried catalyst intermediate into a muffle furnace, roasting the dried catalyst intermediate for 4 hours at 500 ℃, and then naturally cooling the calcined catalyst intermediate;
c) putting the catalyst precursor obtained in the step b) into the filtrate obtained in the step a), soaking for 6 hours, and draining;
d) drying the catalyst precursor obtained in the step c) at 120 ℃ for 12 hours, then putting the dried catalyst precursor into a muffle furnace to be roasted at 500 ℃ for 4 hours, and then naturally cooling to obtain Al
2O
3-TiO
2A supported metal catalyst.
The present invention also provides a process for synthesizing N-methylmorpholine, including:
1) activation and reduction of the supported metal catalyst: 20ml of the supported metal catalyst prepared in example 1 was charged in a fixed bed reactor having a capacity of 80 ml. Then replacing the air in the system with nitrogen, gradually heating to 180 ℃ under the condition of keeping nitrogen flow after replacement, and then gradually raising the reduction temperature; meanwhile, the hydrogen proportion is increased until all hydrogen is contained, the hydrogen flow rate is finally controlled to be 160ml/min, the reduction temperature is 290 ℃, the pressure in the system is controlled to be 0.2MPa, and the total reduction time is 12 hours.
2) Gas-solid phase reaction: morpholine and methanol are mixed according to a molar ratio of 1: 4 adding the mixture into a batching tank, feeding the mixed solution of morpholine and methanol into the upper vaporizing section of the fixed bed reactor for vaporization, then feeding the mixed solution and hydrogen with the flow rate of 60ml/min into a catalyst bed layer according to the space velocity of 0.2g/h/ml, and reacting at the temperature of 180 ℃ and the pressure of 0.8 MPa.
After the reaction is finished, the reaction product is subjected to gas-liquid separation after being condensed; distilling the separated liquid product to recover methanol, adding a water absorbent to remove water, rectifying at normal pressure, collecting 115-117 ℃ fraction as an N-methylmorpholine product, taking the rest fraction as a recycled raw material, and adding methanol for reaction in a circulating manner.
The product content of N-methylmorpholine was 96.7% and the conversion of morpholine was 99.2% by gas chromatography.
Example 2
The embodiment provides a synthesis process of N-methylmorpholine, which comprises the following steps:
the supported metal catalyst was activated and reduced in the same manner as in example 1, followed by gas-solid reaction.
Gas-solid phase reaction: morpholine and methanol are mixed according to a molar ratio of 1: 6, adding the mixture into a batching tank, feeding the mixed solution of morpholine and methanol into the upper vaporization section of the fixed bed reactor for vaporization, and then feeding the mixed solution and hydrogen with the flow rate of 60ml/min into a catalyst bed layer for reaction at the temperature of 190 ℃ and the pressure of 0.9MPa according to the space velocity of 0.3 g/h/ml.
After the reaction is finished, the reaction product is subjected to gas-liquid separation after being condensed; distilling the separated liquid product to recover methanol, adding a water absorbent to remove water, rectifying at normal pressure, collecting 115-117 ℃ fraction as an N-methylmorpholine product, taking the rest fraction as a recycled raw material, and adding methanol for reaction in a circulating manner.
The product content of N-methylmorpholine was 97.3% and the conversion of morpholine was 99.5% by gas chromatography.
Example 3
This example provides a supported metal catalyst comprising Al
2O
3-TiO
2Carrier and carrier supported on Al
2O
3-TiO
2The active metal of the carrier accounts for 24.31 percent of the mass of the supported metal catalyst.
The active metals include Ni, Cu, La and Co. Wherein the mass of Ni accounts for 6.56% of the mass of the supported metal catalyst; the mass of Cu accounted for 14.26%, the mass of La accounted for 3.43%, and the mass of La accounted for 0.06% of the mass of the supported metal catalyst.
This embodiment also provides a method for preparing a supported metal catalyst, which comprises:
a) 71.50g of copper nitrate, 41.80g of nickel nitrate, 22.60g of cobalt nitrate and 0.25g of lanthanum nitrate are dissolved in 100ml of distilled water, and the volume is determined to be the nitrate water-soluble solution with the required concentrationLiquid is reserved; mixing 40g clover type Al
2O
3-TiO
2Soaking the carrier in 100ml of solution for 8 hours, and then filtering to obtain filtrate and a catalyst;
steps b), c) and d) correspond to example 1. With the difference that the time for the first impregnation was 8 hours and the conditions for the first drying were: at 130 ℃ for 11 hours; the conditions of the first roasting are as follows: 5.0 hours at 550 ℃; the time of the second impregnation is 8 hours, and the conditions of the second drying are as follows: at 130 ℃ for 11 hours; the conditions of the second roasting are as follows: 500 ℃ for 3.0 hours.
The present invention also provides a process for synthesizing N-methylmorpholine, including:
the supported metal catalyst was activated and reduced in the same manner as in example 1, followed by gas-solid reaction.
Gas-solid phase reaction: morpholine and methanol are mixed according to a molar ratio of 1: 4 adding the mixture into a batching tank, feeding the mixed solution of morpholine and methanol into the upper vaporizing section of the fixed bed reactor for vaporization, and then feeding the mixed solution and hydrogen with the flow rate of 60ml/min into a catalyst bed layer for reaction at the temperature of 170 ℃ and the pressure of 0.7MPa according to the space velocity of 0.15 g/h/ml.
After the reaction is finished, the reaction product is subjected to gas-liquid separation after being condensed; distilling the separated liquid product to recover methanol, adding a water absorbent to remove water, rectifying at normal pressure, collecting 115-117 ℃ fraction as an N-methylmorpholine product, taking the rest fraction as a recycled raw material, and adding methanol for reaction in a circulating manner.
The product content of N-methylmorpholine was 97.4% and the conversion of morpholine was 99.6% by gas chromatography.
Example 4
The embodiment provides a synthesis process of N-methylmorpholine, which comprises the following steps:
the supported metal catalyst was activated and reduced in the same manner as in example 1, followed by gas-solid reaction.
Gas-solid phase reaction: morpholine and methanol are mixed according to a molar ratio of 1: 6, adding the mixture into a batching tank, feeding the mixed solution of morpholine and methanol into the upper vaporizing section of the fixed bed reactor for vaporization, and then feeding the mixed solution and hydrogen with the flow rate of 60ml/min into a catalyst bed layer for reaction at the temperature of 180 ℃ and the pressure of 0.85MPa according to the space velocity of 0.3 g/h/ml.
After the reaction is finished, the reaction product is subjected to gas-liquid separation after being condensed; distilling the separated liquid product to recover methanol, adding a water absorbent to remove water, rectifying at normal pressure, collecting 115-117 ℃ fraction as an N-methylmorpholine product, taking the rest fraction as a recycled raw material, and adding methanol for reaction in a circulating manner.
The product content of N-methylmorpholine was 98.2% and the conversion of morpholine was 99.8% by gas chromatography.
Example 5
This example provides a supported metal catalyst comprising Al
2O
3-TiO
2Carrier and carrier supported on Al
2O
3-TiO
2The active metal of the carrier accounts for 15.29 percent of the mass of the supported metal catalyst.
The active metals include Ni and Cu. Wherein the mass of Ni accounts for 5.03% of the mass of the supported metal catalyst; the mass of Cu accounted for 10.26% of the mass of the supported metal catalyst.
This embodiment also provides a method for preparing a supported metal catalyst, which comprises:
a) dissolving 51.64g of copper nitrate and 33.05g of nickel nitrate in 100ml of distilled water, and fixing the volume to obtain a nitrate aqueous solution with the required concentration for later use; mixing 40g clover type Al
2O
3-TiO
2Soaking the carrier in 100ml of solution for 6 hours, and then filtering to obtain filtrate and a catalyst;
steps b), c) and d) correspond to example 1.
The present invention also provides a process for synthesizing N-methylmorpholine, including:
the supported metal catalyst was activated and reduced by the method of example 1, and then subjected to a gas-solid reaction, and the method was the same as in example 1.
The product content of N-methylmorpholine was 94.8% and the conversion of morpholine was 98.1% by gas chromatography.
Example 6
This example provides a supported metal catalyst comprising Al
2O
3-TiO
2Carrier and carrier supported on Al
2O
3-TiO
2The active metal of the carrier accounts for 29.21 percent of the mass of the supported metal catalyst.
The active metals include Ni, Cu, Co and La. Wherein the mass of Ni accounts for 9.63% of the mass of the supported metal catalyst; the mass of Cu accounted for 14.45% of the mass of the supported metal catalyst, the mass of Co accounted for 4.94% of the mass of the supported metal catalyst, and the mass of La accounted for 0.19% of the mass of the supported metal catalyst.
This embodiment also provides a method for preparing a supported metal catalyst, which comprises:
a) dissolving 71.77g of copper nitrate, 63.28g of nickel nitrate, 32.50g of cobalt nitrate and 0.79g of lanthanum nitrate in 100ml of distilled water, and fixing the volume to a nitrate aqueous solution with required concentration for later use; mixing 40g clover type Al
2O
3-TiO
2Soaking the carrier in 100ml of solution for 6 hours, and then filtering to obtain filtrate and a catalyst;
steps b), c) and d) correspond to example 1.
The present invention also provides a process for synthesizing N-methylmorpholine, including:
the supported metal catalyst was activated and reduced by the method of example 1, and then subjected to a gas-solid reaction, and the method was the same as in example 1.
The product content of N-methylmorpholine was 98.4% and the conversion of morpholine was 99.7% by gas chromatography.
Example 7
This example provides a supported metal catalyst comprising Al
2O
3-TiO
2Carrier and carrier supported on Al
2O
3-TiO
2The active metal of the carrier accounts for 22.28 percent of the mass of the supported metal catalyst.
The active metals include Ni, Cu, La and Co. Wherein the mass of Ni accounts for 6.06% of the mass of the supported metal catalyst; the mass of Cu accounted for 13.14% of the mass of the supported metal catalyst, the mass of La accounted for 3.03% of the mass of the supported metal catalyst, and the mass of La accounted for 0.05% of the mass of the supported metal catalyst.
This embodiment also provides a method for preparing a supported metal catalyst, which comprises:
a) dissolving 71.50g of copper nitrate, 41.80g of nickel nitrate, 22.60g of cobalt nitrate and 0.25g of lanthanum nitrate in 100ml of distilled water, and fixing the volume to obtain a nitrate aqueous solution with the required concentration for later use; mixing 40g clover type Al
2O
3-TiO
2Soaking the carrier in 100ml of solution for 8 hours, and then filtering to obtain filtrate and a catalyst;
steps b), c) and d) correspond to example 1. With the difference that the time for the first impregnation was 7 hours and the conditions for the first drying were: 110 ℃ for 13 hours; the conditions of the first roasting are as follows: 500 ℃ for 3.0 hours; the time of the second impregnation was 7 hours, and the conditions of the second drying were: at 130 ℃ for 11 hours; the conditions of the second roasting are as follows: 500 ℃ for 5.0 hours
The present invention also provides a process for synthesizing N-methylmorpholine, including:
the supported metal catalyst was activated and reduced in the same manner as in example 1, followed by gas-solid reaction.
Gas-solid phase reaction: morpholine and methanol are mixed according to a molar ratio of 1: 4 adding the mixture into a batching tank, feeding the mixed solution of morpholine and methanol into the upper vaporizing section of the fixed bed reactor for vaporization, and then feeding the mixed solution and hydrogen with the flow rate of 60ml/min into a catalyst bed layer for reaction at the temperature of 170 ℃ and the pressure of 0.7MPa according to the space velocity of 0.15 g/h/ml.
After the reaction is finished, the reaction product is subjected to gas-liquid separation after being condensed; distilling the separated liquid product to recover methanol, adding a water absorbent to remove water, rectifying at normal pressure, collecting 115-117 ℃ fraction as an N-methylmorpholine product, taking the rest fraction as a recycled raw material, and adding methanol for reaction in a circulating manner.
The product content of N-methylmorpholine was 96.1% and the conversion of morpholine was 99.1% by gas chromatography.
Example 8
This example provides a supported metal catalyst and the same method of preparation as example 1.
The present invention also provides a process for synthesizing N-methylmorpholine, including:
1) activation and reduction of the supported metal catalyst: 20ml of the supported metal catalyst prepared in example 1 was charged in a fixed bed reactor having a capacity of 80 ml. Then replacing the air in the system with nitrogen, gradually heating to 160 ℃ under the condition of keeping nitrogen flow after replacement, and then gradually raising the reduction temperature; meanwhile, the hydrogen proportion is increased until all hydrogen is contained, the hydrogen flow rate is finally controlled to be 160ml/min, the reduction temperature is 295 ℃, the pressure in the system is controlled to be 0.25MPa, and the total reduction time is 10 hours.
2) Gas-solid phase reaction: the same as in example 1.
The product content of N-methylmorpholine was 96.2% and the conversion of morpholine was 98.5% by gas chromatography.
Example 9
This example provides a supported metal catalyst and the same method of preparation as example 1.
The present invention also provides a process for synthesizing N-methylmorpholine, including:
1) activation and reduction of the supported metal catalyst: 20ml of the supported metal catalyst prepared in example 1 was charged in a fixed bed reactor having a capacity of 80 ml. Then replacing the air in the system with nitrogen, gradually heating to 170 ℃ under the condition of keeping nitrogen flow after replacement, and then gradually increasing the reduction temperature; meanwhile, the hydrogen proportion is increased until all hydrogen is contained, the hydrogen flow rate is finally controlled to be 160ml/min, the reduction temperature is 300 ℃, the pressure in the system is controlled to be 0.30MPa, and the total reduction time is 11 hours.
2) Gas-solid phase reaction: the same as in example 1.
The product content of N-methylmorpholine was 96.6% and the conversion of morpholine was 99.3% by gas chromatography.
Example 10
The embodiment provides a synthesis process of N-methylmorpholine, which comprises the following steps:
the supported metal catalyst was activated and reduced in the same manner as in example 1, followed by gas-solid reaction.
Gas-solid phase reaction: morpholine and methanol are mixed according to a molar ratio of 1:1, adding the mixture into a batching tank, feeding the mixed solution of morpholine and methanol into the upper vaporization section of the fixed bed reactor for vaporization, and then feeding the mixed solution and hydrogen with the flow rate of 60ml/min into a catalyst bed layer for reaction at the temperature of 180 ℃ and the pressure of 1.2MPa according to the space velocity of 0.1 g/h/ml.
After the reaction is finished, the reaction product is subjected to gas-liquid separation after being condensed; distilling the separated liquid product to recover methanol, adding a water absorbent to remove water, rectifying at normal pressure, collecting 115-117 ℃ fraction as an N-methylmorpholine product, taking the rest fraction as a recycled raw material, and adding methanol for reaction in a circulating manner.
The product content of N-methylmorpholine was 96.9% and the conversion of morpholine was 99.2% by gas chromatography.
Comparative example 1:
this comparative example provides a supported metal catalyst comprising Al
2O
3Carrier and carrier supported on Al
2O
3The active metal of the carrier accounts for 24.37 percent of the mass of the supported metal catalyst.
The active metals include Ni, Cu and La. Wherein the mass of Ni accounts for 7.42% of the mass of the supported metal catalyst; the mass of Cu accounted for 16.87% of the mass of the supported metal catalyst, and the mass of La accounted for 0.08% of the mass of the supported metal catalyst.
The comparative example provides a method for preparing a supported metal catalyst that operates and conditions identical to the method for preparing a supported metal catalyst provided in example 1, except that 40g of clover type Al was used
2O
3Support (instead of Al)
2O
3-TiO
2) Soaking the carrier into 100ml of solution for 6 hours, and then draining to obtain filtrate and a catalyst intermediate;
n-methylmorpholine was prepared using the supported metal catalyst of this comparative example following the N-methylmorpholine synthesis procedure provided in example 1, with a 95.4% N-methylmorpholine product and a 86.2% morpholine conversion by gas chromatography.
Comparative example 2:
this comparative example provides a supported metal catalyst comprising Al
2O
3Carrier and carrier supported on Al
2O
3The active metal of the carrier accounts for 29.21 percent of the mass of the supported metal catalyst.
The active metal comprises Ni, Cu, Co and La. Wherein the mass of Ni accounts for 9.63% of the mass of the supported metal catalyst; the mass of Cu accounted for 14.45% of the mass of the supported metal catalyst, the mass of Co accounted for 4.94% of the mass of the supported metal catalyst, and the mass of La accounted for 0.19% of the mass of the supported metal catalyst.
This comparative example provides a method of preparing a supported metal catalyst that operates and conditions identical to the method of preparing the supported metal catalyst provided in example 1, except that the starting materials were 71.77g of copper nitrate, 63.28g of nickel nitrate, 32.50g of cobalt nitrate, and 0.79g of lanthanum nitrate.
N-methylmorpholine was prepared using the supported metal catalyst of this comparative example following the N-methylmorpholine synthesis procedure provided in example 1, with a product N-methylmorpholine content of 95.7% and a morpholine conversion of 90.4% as determined by gas chromatography.
Comparative example 3:
this comparative example provides a supported metal catalyst comprising Al
2O
3Carrier and carrier supported on Al
2O
3The active metal of the carrier accounts for 41.51 percent of the mass of the supported metal catalyst.
The active metal comprises Ni, Cu, Co and La. Wherein the mass of Ni accounts for 14.63% of the mass of the supported metal catalyst; the mass of Cu accounted for 21.75% of the mass of the supported metal catalyst, the mass of Co accounted for 4.94% of the mass of the supported metal catalyst, and the mass of La accounted for 0.19% of the mass of the supported metal catalyst.
This comparative example provides a method of preparing a supported metal catalyst that operates and conditions identical to the method of preparing the supported metal catalyst provided in example 1, except that the starting materials were 110.47g of copper nitrate, 96.12g of nickel nitrate, 32.50g of cobalt nitrate, and 0.79g of lanthanum nitrate.
N-methylmorpholine was prepared using the supported metal catalyst of this comparative example following the N-methylmorpholine synthesis procedure provided in example 1, with a product N-methylmorpholine content of 95.9% and a morpholine conversion of 94.7% by gas chromatography.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A supported metal catalyst comprising Al
2O
3-TiO
2Carrier and Al supported on the carrier
2O
3-TiO
2Active metal of a carrier, wherein the mass of the active metal accounts for 15-30% of the mass of the supported metal catalyst.
2. The supported metal catalyst of claim 1, wherein the active metal comprises at least two of Ni, Cu, Co, Zn and La;
preferably, the active metal includes at least Cu and Ni;
preferably, the active metals include Ni, Cu, and Co;
preferably, the active metal includes Ni, Cu, and La.
3. The supported metal catalyst of claim 2, wherein when the active metal comprises Cu, the mass of Cu comprises 10-20% of the mass of the supported metal catalyst;
preferably, when the active metal comprises Ni, the mass of Ni accounts for 5-10% of the mass of the supported metal catalyst;
preferably, the mass of Zn accounts for 0-10% of the mass of the supported metal catalyst;
preferably, the mass of Co accounts for 0-5% of the mass of the supported metal catalyst;
preferably, the mass of La accounts for 0-0.2% of the mass of the supported metal catalyst.
4. The supported metal catalyst of any one of claims 1-3, wherein the Al is
2O
3-TiO
2The shape of the carrier is any one of a cylinder, a hollow cylinder, a sphere, a clover and a clover; preferred are clover type and hollow cylinder type.
5. The method of preparing a supported metal catalyst of any of claims 1-4, comprising: in Al
2O
3-TiO
2The carrier is loaded with active metal.
6. The method according to claim 5, wherein the Al is impregnated by a secondary impregnation method
2O
3-TiO
2Supporting the active metal on a carrier;
preferably, the secondary impregnation method comprises impregnating the Al
2O
3-TiO
2The carrier is immersed in a salt solution containing active metals for the first immersion, and then the first drying and the first roasting are carried out; then adding the Al
2O
3-TiO
2The carrier is soaked in a salt solution containing active metal for the second soaking, and then the second drying and the second roasting are carried out;
preferably, the salt solution containing the active metal is a nitrate solution;
preferably, the mass concentration of the nitrate solution is 10-40%;
preferably, the nitrate solution is Ni (NO)
3)
2、Cu(NO
3)
2、Co(NO
3)
2、Zn(NO
3)
2And La (NO)
3)
3A mixed solution of at least two of (1);
preferably, the time of the first impregnation is 6 to 8 hours, and the conditions of the first drying are as follows: 110 ℃ and 130 ℃ for 11-13 hours; the conditions of the first roasting are as follows: 400-550 ℃ for 3.0-5.0 hours;
preferably, the time of the second impregnation is 6 to 8 hours, and the conditions of the second drying are as follows: 110 ℃ and 130 ℃ for 11-13 hours; the conditions of the second roasting are as follows: 400-550 ℃ for 3.0-5.0 hours.
7. Use of a supported metal catalyst as defined in any one of claims 1 to 4 or as prepared by the method of preparation of a supported metal catalyst as defined in claim 5 or 6 for the catalytic synthesis of N-methylmorpholine.
8. A synthesis process of N-methylmorpholine is characterized by comprising the following steps: carrying out a catalytic reaction to form the N-methylmorpholine by using the supported metal catalyst according to any one of claims 1-4 or the supported metal catalyst prepared by the method of preparing the supported metal catalyst according to claim 5 or 6.
9. The process of claim 8, wherein the catalytic reaction comprises: under the atmosphere of reducing gas, the supported metal catalyst is used for catalyzing morpholine and methanol to carry out gas-solid phase reaction;
preferably, the molar ratio of morpholine to methanol is 1: 1-6;
preferably, the conditions under which the gas-solid reaction is carried out are: the pressure is 0.6-1.2MPa, and the temperature is 150-;
preferably, the gas-solid phase reaction is carried out with morpholine and methanol as gases, and the space velocity of the mixed gas formed by morpholine and methanol is 0.1-0.3 g/h/ml;
preferably, after the reaction is finished, post-treatment is carried out;
preferably, the post-treatment comprises the steps of sequentially carrying out gas-liquid separation after the reaction is finished to form a liquid product, then removing methanol and water, and then rectifying to form the N-methylmorpholine;
preferably, the reducing gas is hydrogen;
preferably, the flow rate of hydrogen is 60-80 ml/min.
10. The process according to claim 9, further comprising activating and reducing the supported metal catalyst before the gas-solid phase reaction;
preferably, the activation reduction of the supported metal catalyst comprises: adding the supported metal catalyst into a fixed bed, replacing air in the fixed bed by using inert gas, increasing the temperature to 160-;
preferably, the total activation reduction time is 10-12 hours.
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Cited By (1)
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