CN111892555A - Morpholine production system - Google Patents

Morpholine production system Download PDF

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Publication number
CN111892555A
CN111892555A CN202010808384.5A CN202010808384A CN111892555A CN 111892555 A CN111892555 A CN 111892555A CN 202010808384 A CN202010808384 A CN 202010808384A CN 111892555 A CN111892555 A CN 111892555A
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morpholine
production system
diethylene glycol
solution
hydrogen
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黄凤翔
杨俊�
袁波
石飞
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Sichuan Hongpeng New Material Co ltd
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Sichuan Hongpeng New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to the field of morpholine production, and discloses a morpholine production system. The modified palladium catalyst provided by the invention has high activity, high stability and high selectivity, and can greatly improve the catalytic activity of the reaction and improve the reaction efficiency; on the other hand, the condenser, the decarbonizer, the deamination tower, the morpholine rectifying tower and the diethylene glycol rectifying tower are sequentially utilized in the production process, the hydrogen, the liquid ammonia and the diethylene glycol are separated out and returned to the production system again for recycling, the production cost is greatly reduced, the economic benefit is improved, and meanwhile, the pollution to the environment is reduced.

Description

Morpholine production system
Technical Field
The invention relates to the technical field of morpholine production, in particular to a morpholine production system.
Background
Morpholine (morpholinone), also known as Morpholine or 1, 4-oxaazacyclohexaneMolecular formula C4H9NO, one of industrially important cyclic amines, is a colorless, water-absorbing oily liquid, and is a mild base. Morpholine contains secondary amine groups, with all the typical reaction characteristics of a secondary amine group. Because of the characteristics of nitrogen-oxygen heterocycle, morpholine occupies an important position in chemical production, is an intermediate for manufacturing a plurality of fine chemical products, and becomes one of the fine petrochemical products with important commercial application at present. The preparation method can be used for preparing rubber vulcanization accelerators and rust inhibitors such as NOBS, OTOS and the like, preservatives, surfactants, detergent analgesics, local anesthetics, fruit preservatives, textile printing and dyeing auxiliaries and the like, and has wide application in the fields of rubber, medicines, pesticides, dyes, coatings and the like.
The synthetic route of morpholine can be divided into a diethanolamine dehydration method, a dicyanomethyl ether catalytic hydrogenation method, an ethylene oxide catalytic ammoniation method, a dichloroethyl ether dechlorination ammoniation cyclization method, an amine dehydration cyclization method, a diethylene glycol catalytic ammonolysis cyclization method and the like according to different raw materials. The diethanolamine raw material required by the diethanolamine method is expensive, the reaction yield is low, the production cost is high, and the product has no competitiveness; so that the morpholine is prepared by diethylene glycol and ammonia under the condition of hydrogen and in the presence of a catalyst in the industry, on one hand, in the existing morpholine production system, the activity, selectivity, service life and the like of the catalyst are relatively low, so that the reaction is incomplete and the reaction efficiency is not high; on the other hand, in the traditional method for producing morpholine by adopting a normal pressure method, the production system basically only pursues the acquisition of morpholine, and the waste gas and waste generated in the production process are basically and completely discharged, so that not only is the environment polluted, but also the waste of raw materials is caused, and the economic benefit is influenced.
Disclosure of Invention
The invention aims to provide a morpholine production system, which uses a modified palladium catalyst to ensure more complete reaction and higher reaction efficiency; meanwhile, the hydrogen, the liquid ammonia and the diglycol are recycled in the production process, so that the production cost is greatly reduced, the economic benefit is improved, and the pollution to the environment is reduced.
The embodiment of the invention is realized by the following steps:
a morpholine production system takes diethylene glycol and liquid ammonia as raw materials, adopts a low-pressure gas phase method under the conditions of hydrogen and a modified palladium catalyst, separates gas-phase hydrogen from liquid-phase ammonia after condensation, decarburization and deamination, and obtains diethylene glycol and morpholine through continuous rectification separation.
Further, the modified palladium catalyst is a Pd-Cu-metal organic framework.
Further, the preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing a salt solution, a metal organic framework and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B while stirring, and heating in a water bath to obtain a gel;
s4, preparing the Pd-Cu-metal organic framework catalyst through drying and heat treatment.
The invention has the beneficial effects that:
the modified palladium catalyst provided by the invention has high activity, high stability and high selectivity, and can greatly improve the catalytic activity of the reaction and improve the reaction efficiency; on the other hand, the condenser, the decarbonizer, the deamination tower, the morpholine rectifying tower and the diethylene glycol rectifying tower are sequentially utilized in the production process, the hydrogen, the liquid ammonia and the diethylene glycol are separated out and returned to the production system again for recycling, the production cost is greatly reduced, the economic benefit is improved, and meanwhile, the pollution to the environment is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic process flow diagram of a morpholine production system according to an embodiment of the present invention.
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 morpholine production system provided by the embodiment of the invention is specifically explained below.
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, adopts a low-pressure gas phase method under the conditions of hydrogen and a modified palladium catalyst, separates gas-phase hydrogen from liquid-phase ammonia after condensation, decarburization and deamination, and obtains diethylene glycol and morpholine through continuous rectification separation.
The method utilizes diethylene glycol and ammonia in a certain proportion to synthesize morpholine in a fixed bed adiabatic reactor under the existence of a modified palladium catalyst and hydrogen, the modified palladium catalyst greatly improves catalytic activity and service life, and is beneficial to high-efficiency reaction. In addition, the reaction by-products, namely the purified N-methylmorpholine and N-ethylmorpholine can be sold as finished products to generate considerable benefits, and the production benefits are improved.
In this embodiment, the diethylene glycol is pumped into the fixed bed adiabatic reactor through the vaporizer, the liquid ammonia and the hydrogen are pumped into the vaporizer through the heater and then are pumped into the fixed bed adiabatic reactor together with the diethylene glycol for reaction, the rear end of the fixed bed adiabatic reactor is sequentially connected with the condenser, the decarbonizer, the deamination device, the morpholine rectifying tower and the diethylene glycol rectifying tower, the diethylene glycol is obtained after being rectified by the diethylene glycol rectifying tower, and the diethylene glycol can be returned to the production system for recycling, so that the production cost is greatly reduced, and the pollution to the environment caused by direct emission is reduced.
In this embodiment, the molar ratio of the diethylene glycol, the liquid ammonia and the hydrogen is: 1: 5-10: 30-50.
In this example, the reaction temperature is 200 ℃ and 260 ℃, the reaction pressure is 1.4-1.7MPa,
in this example, the modified palladium catalyst was a Pd-Cu-metal organic framework.
In this embodiment, the metal-organic framework is selected from MIL-101 or MOFs. The MIL-101 or MOFs can be repeatedly used, has high porosity and surface area, is easy to adjust and functionalize pore channels, and has excellent stability in water, air and common organic solvents, so that the MIL-101 or MOFs has unique superiority in heterogeneous catalysis.
The invention obtains the modified catalyst by grafting Pd-Cu by using the metal organic framework, is applied to the production process of morpholine, has higher activity and selectivity in the catalytic reaction, and on one hand, Cr on the framework3+The Pd-Cu particles are catalytic active sites for reaction, and the catalytic performance and selectivity can be improved by utilizing the synergistic effect between Pd and Cu; on the other hand, the Pd-Cu particles can be coated in the cage framework structure of the metal organic framework, so that the Pd-Cu exists more stably in the cage framework structure of the metal organic framework, the agglomeration phenomenon is avoided, the catalytic activity is improved, the service life is prolonged, the Pd-Cu particles can be repeatedly used in a production system for many times, and the stable performance, high selectivity and catalytic activity can be kept.
In this embodiment, the preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing a salt solution, a metal organic framework and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B while stirring, and heating in a water bath to obtain a gel;
s4, preparing the Pd-Cu-metal organic framework catalyst through drying and heat treatment.
In this embodiment, in the step S3, an oven is used for drying, the drying temperature is 40 ℃ to 100 ℃, and the drying time is 1h to 3 h;
in this embodiment, in step S4, the drying process includes: drying in an oven at 100-150 deg.c for 8-10 hr to obtain crystal, and grinding to obtain powder; the heat treatment comprises the following steps: roasting in a muffle furnace at 300-500 deg.c for 1-3 hr.
Example 1
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein the mol ratio of the diethylene glycol, the liquid ammonia and the hydrogen is 1: 5: 30; the reaction temperature is 200 ℃, and the reaction pressure is 1.4 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing the salt solution, MIL-101 and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 40 ℃ for 3 hours to obtain a gel;
s4, drying by using an oven at 100 ℃ for 10h to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at the roasting temperature of 300 ℃ for 3 hours to prepare the Pd-Cu-MIL-101.
Example 2
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein, the mol ratio of the diglycol, the liquid ammonia and the hydrogen is as follows: 1: 10: 50; the reaction temperature is 260 ℃, and the reaction pressure is 1.7 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing the salt solution, MIL-101 and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 100 ℃ for 3 hours to obtain a gel;
s4, drying by using an oven at the drying temperature of 150 ℃ for 8h to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at 500 ℃ for 1h to prepare the Pd-Cu-MIL-101.
Example 3
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein, the mol ratio of the diglycol, the liquid ammonia and the hydrogen is as follows: 1: 6: 40; the reaction temperature is 210 ℃, and the reaction pressure is 1.5 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing a salt solution, MOFs and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 50 ℃ for 1.5h to obtain a gel;
s4, drying by using an oven at the drying temperature of 110 ℃ for 9 hours to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at 350 ℃ for 2h to prepare the Pd-Cu-MOFs.
Example 4
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein, the mol ratio of the diglycol, the liquid ammonia and the hydrogen is as follows: 1: 7: 35; the reaction temperature is 220 ℃, and the reaction pressure is 1.6 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing a salt solution, MOFs and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 60 ℃ for 2 hours to obtain a gel;
s4, drying by using an oven at the drying temperature of 130 ℃ for 8.5 hours to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at the roasting temperature of 400 ℃ for 1.5h to prepare the Pd-Cu-MOFs.
Example 5
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein, the mol ratio of the diglycol, the liquid ammonia and the hydrogen is as follows: 1: 8: 45; the reaction temperature is 230 ℃, and the reaction pressure is 1.6 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing a salt solution, MOFs and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 70 ℃ for 1.5h to obtain a gel;
s4, drying by using an oven at the drying temperature of 140 ℃ for 9 hours to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at the roasting temperature of 450 ℃ for 2 hours to prepare the Pd-Cu-MOFs.
Example 6
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein, the mol ratio of the diglycol, the liquid ammonia and the hydrogen is as follows: 1: 9: 40; the reaction temperature is 240 ℃, and the reaction pressure is 1.5 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing the salt solution, MIL-101 and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 80 ℃ for 1.5 hours to obtain a gel;
s4, drying by using an oven at the drying temperature of 130 ℃ for 8.5 hours to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at the roasting temperature of 400 ℃ for 2 hours to prepare the Pd-Cu-MIL-101.
Example 7
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein, the mol ratio of the diglycol, the liquid ammonia and the hydrogen is as follows: 1: 7: 45; the reaction temperature is 250 ℃, and the reaction pressure is 1.6 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing the salt solution, MIL-101 and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 90 ℃ for 2 hours to obtain a gel;
s4, drying by using an oven at the drying temperature of 140 ℃ for 9 hours to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at the roasting temperature of 450 ℃ for 1.5h to prepare the Pd-Cu-MIL-101.
Example 8
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein, the mol ratio of the diglycol, the liquid ammonia and the hydrogen is as follows: 1: 9: 40; the reaction temperature is 240 ℃, and the reaction pressure is 1.5 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing the salt solution, MIL-101 and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 80 ℃ for 2 hours to obtain a gel;
s4, drying by using an oven at the drying temperature of 120 ℃ for 8.5 hours to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at the roasting temperature of 400 ℃ for 2 hours to prepare the Pd-Cu-MIL-101.
Example 9
A morpholine production system takes diethylene glycol and liquid ammonia as raw materials, under the condition of hydrogen and a modified palladium catalyst, a low-pressure gas phase method is adopted, gas-phase hydrogen and liquid-phase ammonia are respectively separated through a condenser, a decarbonizer and a deamination tower in sequence, and are treated through a finished product rectifying tower and a diethylene glycol rectifying tower to obtain morpholine and diethylene glycol through separation; wherein, the mol ratio of the diglycol, the liquid ammonia and the hydrogen is as follows: 1: 8: 40; the reaction temperature is 230 ℃, and the reaction pressure is 1.5 MPa.
The preparation method of the modified palladium catalyst comprises the following steps:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing the salt solution, MIL-101 and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B, stirring simultaneously, and heating in a water bath at the temperature of 70 ℃ for 2 hours to obtain a gel;
s4, drying by using an oven at the drying temperature of 130 ℃ for 9 hours to obtain a crystal, and grinding to obtain a powdery object; and roasting the powder in a muffle furnace at the roasting temperature of 400 ℃ for 2 hours to prepare the Pd-Cu-MIL-101.
Examples of the experiments
The catalyst of the morpholine production system of the above example was investigated for its effect on morpholine catalytic performance, as well as for conventional Pd-Cu-AL2O3And the catalyst of single metal grafted on the metal framework,the properties are shown in table 1:
TABLE 1 influence of the catalyst on the catalytic Properties of morpholine
Kind of catalyst Diethylene glycol conversion (%) Morpholine purity (%)
Pd-Cu-MIL-101 99 99.93
Pd-Cu-MIL-MOFs 98 99.89
Pd-MIL-101 89.1 87.2
Pd-MIL-MOFs 88.7 86.6
Cu-MIL-101 87.4 82.1
Cu-MIL-MOFs 85.8 82.4
Pd-Cu-AL2O3 78.9 75.1
As can be seen from the data in Table 1, the modified palladium catalyst provided by the present invention can utilize Cr on the metal skeleton3+And Pd-Cu particles are used as catalytic active sites for reaction, and the catalytic performance and selectivity can be improved by utilizing the synergistic effect between Pd and Cu; on the other hand, the Pd-Cu particles can be coated in the cage framework structure of the metal organic framework, so that the Pd-Cu exists more stably in the cage framework structure of the metal organic framework, the agglomeration phenomenon is avoided, the catalytic activity is improved, the service life is prolonged, the Pd-Cu particles can be repeatedly used in a production system for many times, the stable performance, the high selectivity and the catalytic activity can be kept, the conversion rate of the diethylene glycol can be greatly improved, the reaction is more sufficient and complete, and the purity and the yield of the morpholine product are improved.
In conclusion, the modified palladium catalyst provided by the invention has high activity, high stability and high selectivity, and can greatly improve the catalytic activity of the reaction and improve the reaction efficiency; on the other hand, the condenser, the decarbonizer, the deamination tower, the morpholine rectifying tower and the diethylene glycol rectifying tower are sequentially utilized in the production process, the hydrogen, the liquid ammonia and the diethylene glycol are separated out and returned to the production system again for recycling, the production cost is greatly reduced, the economic benefit is improved, and meanwhile, the pollution to the environment is reduced.
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 morpholine production system is characterized in that diethylene glycol and liquid ammonia are used as raw materials, a low-pressure gas phase method is adopted under the condition of hydrogen and a modified palladium catalyst, gas-phase hydrogen and liquid-phase ammonia are separated after condensation, decarburization and deamination, and diethylene glycol and morpholine are obtained through continuous rectification separation.
2. The morpholine production system according to claim 1, wherein the diethylene glycol is pumped into the fixed bed adiabatic reactor through a vaporizer, and the liquid ammonia and hydrogen are pumped into the vaporizer through a heater and then pumped into the fixed bed adiabatic reactor together with the diethylene glycol for reaction.
3. The morpholine production system according to claim 2, wherein a condenser, a decarboniser, a deamination tower, a finished product rectification tower and a diethylene glycol rectification tower are connected in sequence at the rear end of the fixed bed adiabatic reactor.
4. The morpholine production system of claim 1, wherein the molar ratio of diethylene glycol, liquid ammonia and hydrogen is: 1: 5-10: 30-50.
5. The morpholine production system according to claim 1, wherein the reaction temperature is 200 ℃ and 260 ℃ and the reaction pressure is 1.4-1.7 MPa.
6. The morpholine production system of claim 1, wherein the modified palladium catalyst is a Pd-Cu-metal organic framework.
7. Morpholine production system according to claim 6, characterised in that the metal-organic framework is selected from MIL-101 or MOFs.
8. The morpholine production system of claim 7, wherein the modified palladium catalyst preparation method comprises the steps of:
s1, Pd is to be contained2+Salt solution, Cu2+Uniformly mixing a salt solution, a metal organic framework and a peptizing agent to form a solution A;
s2, uniformly mixing glacial acetic acid, distilled water and a peptizing agent to form a solution B;
s3, mixing the solution A and the solution B while stirring, and heating in a water bath to obtain a gel;
s4, preparing the Pd-Cu-metal organic framework catalyst through drying and heat treatment.
9. The morpholine production system according to claim 8, wherein in step S3, the heating temperature is 40-100 ℃ and the heating time is 1-3 h.
10. The morpholine production system according to claim 8, wherein in step S4, the drying process is: drying in an oven at 100-150 deg.c for 8-10 hr to obtain crystal, and grinding to obtain powder; the heat treatment comprises the following steps: roasting in a muffle furnace at 300-500 deg.c for 1-3 hr.
CN202010808384.5A 2020-08-12 2020-08-12 Morpholine production system Pending CN111892555A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1394030A (en) * 1973-01-18 1975-05-14 Jefferson Chem Co Inc Process for producing highpurity morpholine
CN1569327A (en) * 2004-04-23 2005-01-26 吉化集团公司 Preparation of 1,4-oxygen nitrogen heterocyclic hexane catalyst by ammonification of diethylene glycol and process thereof

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
GB1394030A (en) * 1973-01-18 1975-05-14 Jefferson Chem Co Inc Process for producing highpurity morpholine
CN1569327A (en) * 2004-04-23 2005-01-26 吉化集团公司 Preparation of 1,4-oxygen nitrogen heterocyclic hexane catalyst by ammonification of diethylene glycol and process thereof

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张龙传等: "国内吗啉生产工艺现状", 《中国石油和化工》 *
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