Morpholine Synthesis Process

Abstract

The present invention relates to the technical field of chemical production, and specifically discloses a morpholine synthesis process, comprising the following steps: 1) preheated diethylene glycol, ammonia and hydrogen are passed into a vaporizer, and the vaporized mixed gas enters a reactor, and generates morpholine through a catalyst catalytic reaction at a certain temperature and pressure; 2) step 1) the product enters a gas-liquid separator after heat exchange and condensation, and the separated liquid enters a synthesis intermediate tank; 3) the crude morpholine in the synthesis intermediate tank enters a deamination tower for rectification operation; 4) the product after deamination enters a dehydration tower, and most of water, N-methylmorpholine and N-ethylmorpholine are removed; 5) the product of step 4) enters a light removal tower, and enters a product tower after removing a part of water and impurities, and a high-purity morpholine product is extracted from the product tower. Using this process, the purity of the synthetic morpholine product is high, up to 95mol%.

Description

Technical Field

[0001] The invention relates to the technical field of chemical production, and in particular to a morpholine synthesis process. Background Art

[0002] Morpholine, also known as morpholin, is a colorless oily liquid at room temperature and a strong base. Morpholine contains secondary amine groups and has all the typical reaction characteristics of secondary amine groups. It reacts with inorganic acids to form salts and with organic acids to form salts or amides. It can undergo alkylation reactions and can also react with ethylene oxide, ketones or undergo Willgerodt reactions. Due to its characteristics of nitrogen-oxygen heterocycles, morpholine occupies an important position in chemical production and is an intermediate reagent for the manufacture of many fine chemical products. It has become one of the fine petrochemical products with important commercial uses. It can be used to prepare rubber vulcanization accelerators and rust inhibitors such as NOBS (N-oxydiethylene-2-benthiazole sulfonamide), OTOS (N-oxydiethylenecarbamoyl-N-oxydiethylenesulfonamide), preservatives, surfactants, descaling analgesics, local anesthetics, fruit preservatives, textile printing and dyeing auxiliaries, etc. It is widely used in the fields of rubber, medicine, pesticides, dyes, coatings, etc.

[0003] The synthetic route of morpholine can be divided into diethanolamine dehydration method, dicyanomethyl ether catalytic hydrogenation method, ethylene oxide catalytic amination method, dichloroethyl ether dechlorination amination cyclization method, amine dehydration cyclization method, diethylene glycol catalytic ammonia decyclization method, etc., depending on the raw materials used. Among them, the diethylene glycol catalytic ammonia decyclization method has the advantages of easy availability of raw materials, low price, low toxicity, and less generation of three wastes, and is very suitable for industrial large-scale production. Domestic manufacturers basically use this method.

[0004] In the existing diethylene glycol process for producing morpholine, the products coming out of the gas-liquid separator are mostly directly fed into the deammoniation tower for ammonia recycling. However, the products coming out of the gas-liquid separator may not be well deaminated due to too fast or too slow flow rate and enter the liquid ammonia extraction link, resulting in a low yield of the product morpholine. Summary of the invention

[0005] The purpose of the present invention is to provide a novel morpholine synthesis process in view of the above problems.

[0006] A morpholine synthesis process, characterized in that it comprises the following steps: 1) preheated diethylene glycol, ammonia and hydrogen are introduced into a vaporizer, and the vaporized mixed gas enters a reactor, and generates morpholine through a catalytic reaction under a certain temperature and pressure; 2) the product of step 1) enters a gas-liquid separator after heat exchange and condensation, and the separated liquid enters a synthesis intermediate tank; 3) the crude morpholine in the synthesis intermediate tank enters a deamination tower for rectification operation; 4) the product after deamination enters a dehydration tower to remove most of water, N-methylmorpholine and N-ethylmorpholine; 5) the product of step 4) enters a lightness removal tower, and enters a product tower after removing a part of water and impurities, and a high-purity morpholine product is extracted from the product tower.

[0007] In one example, the molar ratio of diethylene glycol, ammonia and hydrogen in step 1) is 1:(1-26):(1-10). Preferably, the molar ratio of diethylene glycol, ammonia and hydrogen in step 1) is 1:(1-16):(1-10).

[0008] In one example, the reaction temperature in step 1) is 160-250° C., the pressure is 0.5-3.0 MPa, and the diethylene glycol space velocity is 0.05-2.5 L / h.

[0009] In one example, most of the gas coming out of the gas-liquid separator in step 2) is recycled, and a small part is recycled after being vented and hydrogenated as tail gas.

[0010] In one example, the liquid ammonia coming out of the deamination tower in step 3) is returned to the liquid ammonia metering tank for reuse in synthesis; the high boiling products coming out of the product tower are discharged into the high boiling product tank.

[0011] In one example, the flow rate of the crude morpholine from the synthesis intermediate tank entering the deamination tower in step 3) is controlled at 7000-8000 kg / h.

[0012] In one example, the impurities in step 5) include ethylene glycol monomethyl ether.

[0013] In one example, the morpholine product has a purity of up to 95 mol%.

[0014] In one example, the catalyst used in step 1) is a catalyst with a hydrotalcite structure formed by using ZnO / Fe3O4 / γ-Al2O3 as a carrier and loading Ni and Cu active components; wherein the content of each component of the catalyst is 55.8% to 70.2% by weight of ZnO / Fe3O4 / γ-Al2O3, 8% to 15% by weight of Ni, and 20% to 30% by weight of Cu; preferably, the preparation method of the catalyst used in step 1) is: a solution A of a certain concentration is prepared according to a molar ratio of Ni(NO3)2·6H2O and Cu(NO3)26H2O of 1:(1.24 to 3.62) and a molar ratio of Al(NO3)3·9H2O, Zn(NO3)2·6H2O and Fe(NO3)3 of 1:(0.1 to 1.5) to prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after the pH value is controlled to be 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying; then the dried product is ground and calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0015] In one example, the synthesis intermediate tank in step 3) includes a tank body and a skirt seat, wherein the tank body is mounted on the skirt seat; a liquid inlet is arranged on the top of the tank body, and a liquid outlet is arranged on the bottom of the tank body, and the liquid outlet is led out of the liquid through a liquid outlet pipe; one end of the liquid outlet pipe is connected to the liquid outlet, and the other end is mounted on the side wall of the skirt seat and extends out of the side wall of the skirt seat. The liquid outlet is always in a low position, and the liquid is led out of the bottom of the tank body more smoothly. At the same time, the liquid outlet pipe is arranged to extend out of the side wall of the skirt seat, which is more convenient for receiving liquid and is conducive to the pumping out of crude morpholine.

[0016] The beneficial effects of the present invention are:

[0017] 1. In the novel morpholine synthesis process, we adopt to set a synthesis intermediate tank between the gas-liquid separator and the deamination tower, so that the product from the overflow extraction section on the tower bottom liquid level in the intermediate tank can enter the deamination tower for deamination, and the synthesis intermediate tank increases the flow distance of gas and liquid, slowing down or increasing its flow rate; with the buffer of the synthesis intermediate tank, it is convenient to control the flow rate of crude morpholine pumped out into the deamination tower, so that the crude morpholine in the morpholine production process of the present application is fully impurity-removed, the morpholine yield is high, the ammonia recovery amount is high, and the maximum yield of morpholine product can reach 95 mol%;

[0018] 2. In the morpholine production process of the present application, ammonia and hydrogen are recycled and reused, with high raw material utilization and less waste;

[0019] 3. The morpholine production process of the present application adopts a hydrotalcite-like catalyst formed by using ZnO / Fe3O4 / γ-Al2O3 as a carrier and loading Ni and Cu active components. The catalyst has good stability and high catalytic activity, resulting in high morpholine yield and good diethylene glycol selectivity;

[0020] 4. The preparation method of the catalyst of the present application adopts a simple hydrothermal method plus drying, grinding and roasting process. The process is simple and easy to control, and the obtained product has good stability;

[0021] 5. The synthetic intermediate tube of the present application has good stability and durability, and the liquid discharge is smooth. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is an overall view of the synthesis intermediate tank of the present invention;

[0023] Figure 2 for Figure 1 Top view of the synthesis intermediate tank;

[0024] Figure 3 for Figure 1 A in the enlarged view;

[0025] Figure 4 The figure is a process diagram for the synthesis of morpholine in the present invention.

[0026] In the figure, 1. liquid inlet; 2. vent; 3. safety valve port; 4. liquid inlet; 5. pressure gauge interface; 6. liquid outlet; 7. on-site liquid level gauge port; 8. remote liquid level gauge port; 9. spare port 1; 10. spare port 2; 11. vertical section; 12. horizontal section; 13. connecting pipe flange; 14. positioning ring; 15. skirt. DETAILED DESCRIPTION

[0027] First, we designed the structure of the synthesis intermediate tank of this application as follows.

[0028] See also Figure 1 , 2 A synthetic intermediate tank for morpholine production includes a tank body and a skirt 15. The top of the tank body is provided with a liquid inlet 1 and a liquid inlet 4 for liquid to enter, as well as a venting port 2, a safety valve port 3 and a pressure gauge interface 5. The top of the tank body is also provided with a spare port 1 9 and a spare port 2 10 for liquid inlet.

[0029] See also Figure 1 and Figure 2 The side wall of the synthesis intermediate tank is also provided with an on-site level meter port 7 and a remote level meter port 8 for measuring the liquid level. A liquid outlet port 6 is provided at the bottom of the synthesis intermediate tank, and a liquid outlet pipe is connected to the liquid outlet port 6. The liquid outlet end of the liquid outlet pipe is installed on the side wall of the skirt seat 15 and extends out of the side wall of the skirt seat 15.

[0030] See also Figure 3 The liquid outlet pipe in the middle of the synthesis plays a drainage role. The liquid outlet pipe includes a vertical section 11 and a horizontal section 12. The vertical section 11 is connected to the bottom of the tank body, and the end of the horizontal section 12 away from the vertical section is installed on the side wall of the skirt 15 and extends out of the side wall of the skirt. The vertical section 11 is connected to the center of the bottom of the tank body, and the vertical section 11 is connected to the bottom of the tank body through a transition pipe with a diameter larger than the diameter of the liquid outlet pipe. This is because the wall of the tank body is generally thicker. In order to save the material of the liquid outlet pipe, only a short transition pipe with a thicker wall needs to be designed as a transition connection. This transition connection method is simple and practical, and has good sealing. The end of the horizontal section 12 of the liquid outlet pipe away from the vertical section 11 is connected to a pipe flange 13. The pipe flange 13 is used to connect other pipelines to facilitate the execution of the next process.

[0031] See also Figure 3 The horizontal section 12 of the liquid outlet pipe is mounted on the side wall of the skirt 15. A positioning ring 14 is arranged on the side wall of the skirt 15, and the axial length of the positioning ring 14 is greater than the thickness of the side wall of the skirt 15. The horizontal section 12 of the liquid outlet pipe is passed through the positioning ring 14. The positioning ring 14 facilitates the placement of the horizontal section of the liquid outlet pipe, because the side wall of the skirt 15 is generally thin, and the positioning ring 14 has a certain width, which can increase the contact area with the horizontal section 12 and better carry the horizontal section 12 of the liquid outlet pipe.

[0032] In the synthesis intermediate tank, the preferred method of the above connection is welding. Not only the sealing of the liquid outlet pipe and the side wall of the skirt is welded, but also the connection of other pipes with the tank body or skirt can be welded.

[0033] See also Figure 4 The process steps of using the above-mentioned synthesis intermediate tank to synthesize morpholine are as follows:

[0034] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:(1-26):(1-10) and then passing them into a vaporizer, the vaporized mixed gas is passed into a reactor, and catalytically reacts at a temperature of 160-250°C, a pressure of 0.5-3.0 MPa and a diethylene glycol space velocity of 0.05-2.L / h to generate morpholine and other impurities; 2) passing the product of step 1) into a gas-liquid separator after heat exchange and condensation, and the separated liquid is passed into a synthesis intermediate tank; 3) the crude morpholine in the synthesis intermediate tank is then pumped into a deamination tower for rectification operation; 4) the product after deamination is passed into a dehydration tower, and most of water, N-methylmorpholine and N-ethylmorpholine are removed from the top of the tower; 5) the product from the dehydration tower is passed into a lightness removal tower, and after a part of water and impurities are removed, it enters a product tower, and a high-purity morpholine product is extracted from the top of the product tower. Most of the gas separated by the gas-liquid separator is recycled, and a small part is vented as tail gas to wash ammonia and recycled after hydrogen extraction; the liquid ammonia extracted from the top of the deamination tower is returned to the liquid ammonia metering tank for repeated use in synthesis.

[0035] The present invention is described in detail below through specific embodiments.

[0036] Example 1

[0037] (1) Preparation of catalyst

[0038] Weigh 5.8gNi(NO3)2·6H2O, 7.32gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after the pH value is controlled to be 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying; then the dried product is ground and calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0039] (2) Preparation of morpholine

[0040] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and catalytically reacts with the catalyst prepared in (1) at 200°C, 1.8 MPa and a diethylene glycol space velocity of 0.12 L / h to generate morpholine and other impurities; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, and the separated liquid enters a synthesis intermediate tank, most of the gas is recycled, a small part is vented as tail gas to wash ammonia and then After hydrogen extraction, it is recycled; 3) The crude morpholine in the synthesis intermediate tank is pumped into the deamination tower at a flow rate of 7400kg / h for rectification operation, and the liquid ammonia produced from the top of the tower is returned to the liquid ammonia metering tank for repeated use in synthesis; 4) The crude morpholine after deamination enters the dehydration tower, and most of the water, N-methylmorpholine, and N-ethylmorpholine are removed from the top of the tower; 5) The product of step 4) enters the light removal tower, and then enters the product tower after a part of water and impurities are removed from the light removal tower, and the high-purity morpholine product is extracted from the top of the product tower. The high-boiling substances from the product tower are discharged into the high-boiling substance tank.

[0041] Example 2

[0042] (1) Preparation of catalyst

[0043] Weigh 5.8gNi(NO3)2·6H2O, 21.37gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0044] (2) Preparation of morpholine

[0045] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and catalytically reacts with the catalyst prepared in (1) at 200°C, 1.8 MPa and a diethylene glycol space velocity of 0.12 L / h to generate morpholine and other impurities; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, and the separated liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas and washed with ammonia and The crude morpholine in the synthesis intermediate tank is pumped into the deamination tower at a flow rate of 7400kg / h for distillation, and the liquid ammonia produced from the top of the tower is returned to the liquid ammonia metering tank for repeated use in the synthesis; 4) The crude morpholine after deamination enters the dehydration tower, and most of the water, N-methylmorpholine and N-ethylmorpholine are removed from the top of the tower; 5) The product of step 4) enters the light removal tower, and then enters the product tower after a part of water and impurities are removed from the light removal tower, and then enters the product tower, and a morpholine product with higher purity is produced from the top of the product tower.

[0046] Example 3

[0047] (1) Preparation of catalyst

[0048] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na +The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0049] (2) Preparation of morpholine

[0050] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and catalytically reacts with the catalyst prepared in (1) at 200°C, 1.8 MPa and a diethylene glycol space velocity of 0.12 L / h to generate morpholine and other impurities; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, and the liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas to be washed with ammonia and hydrogen 3) The crude morpholine in the synthesis intermediate tank is pumped into the deamination tower at a flow rate of 7400kg / h for distillation, and the liquid ammonia produced from the top of the tower is returned to the liquid ammonia metering tank for repeated use in the synthesis; 4) The crude morpholine after deamination enters the dehydration tower, and most of the water, N-methylmorpholine and N-ethylmorpholine are removed from the top of the tower; 5) The product of step 4) enters the light removal tower, and then enters the product tower after a part of water and impurities are removed from the light removal tower, and a morpholine product with higher purity is produced from the top of the product tower.

[0051] Example 4

[0052] (1) Preparation of catalyst

[0053] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 0.57gZn(NO3)2·6H2O, and 0.13gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0054] (2) Preparation of morpholine

[0055] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:16:10 and passing them into a vaporizer, the vaporized mixed gas enters a reactor, and catalytically reacts with the catalyst prepared in (1) at 200°C, 1.8 MPa and a diethylene glycol space velocity of 0.13 L / h to generate morpholine and other impurities; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, the liquid enters a synthesis intermediate tank, most of the gas is recycled, a small part is discharged as tail gas, and washed with ammonia and provided with 3) The crude morpholine in the synthesis intermediate tank is pumped into the deamination tower at a flow rate of 7400kg / h for distillation, and the liquid ammonia produced at the top of the tower is returned to the liquid ammonia metering tank for repeated use in synthesis; 4) The crude morpholine after deamination enters the dehydration tower, and most of the water, N-methylmorpholine and N-ethylmorpholine are removed from the top of the tower; 5) The product of step 4) enters the light removal tower, and then enters the product tower after a part of water and impurities are removed from the light removal tower, and then enters the product tower, and a morpholine product with higher purity is produced from the top of the product tower.

[0056] Example 5

[0057] (1) Preparation of catalyst

[0058] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 0.86gZn(NO3)2·6H2O, and 0.65gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0059] (2) Preparation of morpholine

[0060] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:1:1 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and catalytically reacts with the catalyst prepared in (1) at 200°C, 1.8 MPa and a diethylene glycol space velocity of 0.12 L / h to generate morpholine and other impurities; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, and the liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas to be washed with ammonia and hydrogen 3) The crude morpholine in the synthesis intermediate tank is pumped into the deamination tower at a flow rate of 7400kg / h for distillation, and the liquid ammonia produced from the top of the tower is returned to the liquid ammonia metering tank for repeated use in the synthesis; 4) The crude morpholine after deamination enters the dehydration tower, and most of the water, N-methylmorpholine and N-ethylmorpholine are removed from the top of the tower; 5) The product of step 4) enters the light removal tower, and then enters the product tower after a part of water and impurities are removed from the light removal tower, and a morpholine product with higher purity is produced from the top of the product tower.

[0061] Example 6

[0062] (1) Preparation of catalyst

[0063] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to make a solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0064] (2) Preparation of morpholine

[0065] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:26:10 and passing them into a vaporizer, the vaporized mixed gas enters a reactor, and catalytically reacts with the catalyst prepared in (1) at 160°C, 1.8 MPa and a diethylene glycol space velocity of 0.12 L / h to generate morpholine and other impurities; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, the liquid enters a synthesis intermediate tank, most of the gas is recycled, a small part is discharged as tail gas, and washed with ammonia and provided with 3) The crude morpholine in the synthesis intermediate tank is pumped into the deamination tower at a flow rate of 7400kg / h for distillation operation, and the liquid ammonia produced at the top of the tower is returned to the liquid ammonia metering tank for repeated use in synthesis; 4) The crude morpholine after deamination enters the dehydration tower, and most of the water, N-methylmorpholine and N-ethylmorpholine are removed from the top of the tower; 5) The product of step 4) enters the light removal tower, and then enters the product tower after a part of water and impurities are removed from the light removal tower, and the morpholine product with higher purity is produced from the top of the product tower.

[0066] Example 7

[0067] (1) Preparation of catalyst

[0068] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0069] (2) Preparation of morpholine

[0070] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:13:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and catalytically reacts with the catalyst prepared in (1) at 250°C, 1.8 MPa and a diethylene glycol space velocity of 0.12 L / h to generate morpholine and other impurities; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, the liquid enters a synthesis intermediate tank, most of the gas is recycled, a small part is discharged as tail gas, and washed with ammonia and The crude morpholine in the synthesis intermediate tank is pumped into the deamination tower at 7400 kg / h for distillation, and the liquid ammonia produced from the top of the tower is returned to the liquid ammonia metering tank for repeated use in synthesis; 4) The crude morpholine after deamination enters the dehydration tower, and most of the water, N-methylmorpholine and N-ethylmorpholine are removed from the top of the tower; 5) The product of step 4) enters the light removal tower, and then enters the product tower after part of the water and impurities are removed from the light removal tower, and the product with higher purity is produced from the top of the product tower.

[0071] Example 8

[0072] (1) Preparation of catalyst

[0073] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0074] (2) Preparation of morpholine

[0075] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and catalytically reacts with the catalyst prepared in (1) at 200°C, 0.5 MPa and a diethylene glycol space velocity of 0.12 L / h to generate morpholine and other impurities; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, and the liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas to be washed with ammonia and hydrogen 3) The crude morpholine in the synthesis intermediate tank is pumped into the deamination tower at a flow rate of 7400kg / h for distillation, and the liquid ammonia produced from the top of the tower is returned to the liquid ammonia metering tank for repeated use in the synthesis; 4) The crude morpholine after deamination enters the dehydration tower, and most of the water, N-methylmorpholine and N-ethylmorpholine are removed from the top of the tower; 5) The product of step 4) enters the light removal tower, and then enters the product tower after a part of water and impurities are removed from the light removal tower, and a morpholine product with higher purity is produced from the top of the product tower.

[0076] Example 9

[0077] (1) Preparation of catalyst

[0078] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0079] (2) Preparation of morpholine

[0080] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and generates morpholine and other impurities through a catalytic reaction at 200°C, 3.0MPa and a diethylene glycol space velocity of 0.12L / h; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, the liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas and recycled after washing ammonia and extracting hydrogen; 3) the crude morpholine in the synthesis intermediate tank enters a deamination tower through a pump at a flow rate of 7400kg / h, performs a rectification operation, and liquid ammonia is extracted from the tower top and returned to the liquid ammonia metering tank for repeated use in synthesis; 4) the crude morpholine after deamination enters a dehydration tower, and most of water, N-methylmorpholine and N-ethylmorpholine are removed from the tower top; 5) the product of step 4) enters a lightness removal tower, and then enters a product tower after a part of water and impurities are removed from the lightness removal tower, and then enters a product tower, and a morpholine product with higher purity is extracted from the top of the product tower.

[0081] Example 10

[0082] (1) Preparation of catalyst

[0083] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0084] (2) Preparation of morpholine

[0085] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and generates morpholine and other impurities through a catalytic reaction at 200°C, 1.8MPa and a diethylene glycol space velocity of 0.05L / h; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, the liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas and recycled after washing ammonia and extracting hydrogen; 3) the crude morpholine in the synthesis intermediate tank enters a deamination tower through a pump at a flow rate of 7400kg / h, performs a rectification operation, and liquid ammonia is extracted from the tower top and returned to the liquid ammonia metering tank for repeated use in synthesis; 4) the crude morpholine after deamination enters a dehydration tower, and most of water, N-methylmorpholine and N-ethylmorpholine are removed from the tower top; 5) the product of step 4) enters a lightness removal tower, and then enters a product tower after a part of water and impurities are removed from the lightness removal tower, and then enters a product tower, and a morpholine product with higher purity is extracted from the top of the product tower.

[0086] Embodiment 11

[0087] (1) Preparation of catalyst

[0088] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0089] (2) Preparation of morpholine

[0090] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and generates morpholine and other impurities through a catalytic reaction at 200°C, 1.8MPa and a diethylene glycol space velocity of 2.5L / h; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, the liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas and recycled after washing ammonia and extracting hydrogen; 3) the crude morpholine in the synthesis intermediate tank enters a deamination tower through a pump at a flow rate of 7400kg / h, performs a rectification operation, and liquid ammonia is extracted from the tower top and returned to the liquid ammonia metering tank for repeated use in synthesis; 4) the crude morpholine after deamination enters a dehydration tower, and most of water, N-methylmorpholine and N-ethylmorpholine are removed from the tower top; 5) the product of step 4) enters a lightness removal tower, and then enters a product tower after a part of water and impurities are removed from the lightness removal tower, and then enters a product tower, and a morpholine product with higher purity is extracted from the top of the product tower.

[0091] Example 12

[0092] (1) Preparation of catalyst

[0093] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven to dry for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0094] (2) Preparation of morpholine

[0095] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and generates morpholine and other impurities through a catalytic reaction at 200°C, 1.8MPa and a diethylene glycol space velocity of 0.12L / h; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, the liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas and recycled after washing ammonia and extracting hydrogen; 3) the crude morpholine in the synthesis intermediate tank enters a deamination tower through a pump at a flow rate of 7000kg / h, performs a rectification operation, and liquid ammonia is produced from the tower top and returned to the liquid ammonia metering tank for repeated use in synthesis; 4) the crude morpholine after deamination enters a dehydration tower, and most of water, N-methylmorpholine and N-ethylmorpholine are removed from the tower top; 5) the tower bottom enters a lightness removal tower, and then a part of water and impurities are removed from the lightness removal tower, and then enters a product tower, and a morpholine product with high purity is produced from the top of the product tower.

[0096] Example 13

[0097] (1) Preparation of catalyst

[0098] Weigh 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)26H2O, and 1.39gFe(NO3)3 to prepare solution A of a certain concentration; then prepare Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise in parallel to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred into a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water to a pH value of 7, and then placed in a 120°C oven for drying for 3 hours; then calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst.

[0099] (2) Preparation of morpholine

[0100] 1) preheating diethylene glycol, ammonia and hydrogen in a molar ratio of 1:8:5 and then passing them into a vaporizer, the vaporized mixed gas enters a reactor, and generates morpholine and other impurities through a catalytic reaction at 200°C, 1.8MPa and a diethylene glycol space velocity of 0.12L / h; 2) the reaction product enters a gas-liquid separator after heat exchange, condensation and cooling, the liquid enters a synthesis intermediate tank, most of the gas is recycled, and a small part is discharged as tail gas and recycled after washing ammonia and extracting hydrogen; 3) the crude morpholine in the synthesis intermediate tank enters a deamination tower through a pump at a flow rate of 8000kg / h, performs a rectification operation, and liquid ammonia is extracted from the tower top and returned to the liquid ammonia metering tank for repeated use in synthesis; 4) the crude morpholine after deamination enters a dehydration tower, and most of water, N-methylmorpholine and N-ethylmorpholine are removed from the tower top; 5) the product of step 4) enters a lightness removal tower, and then enters a product tower after a part of water and impurities are removed from the lightness removal tower, and then enters a product tower, and a morpholine product with higher purity is extracted from the top of the product tower.

[0101] Comparative Example 1

[0102] The difference between Comparative Example 1 and Example 1 is that the configuration of Solution A is to weigh 5.8gNi(NO3)2·6H2O, 5.9gCu(NO3)2·6H2O and 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare Solution A of a certain concentration.

[0103] Comparative Example 2

[0104] The difference between Comparative Example 2 and Example 1 is that the configuration of Solution A is to weigh 5.8gNi(NO3)2·6H2O, 22.43gCu(NO3)2·6H2O and 7.2gAl(NO3)3·9H2O, 5.7gZn(NO3)2·6H2O, and 1.39gFe(NO3)3 to prepare Solution A of a certain concentration.

[0105] Comparative Example 3

[0106] The difference between this embodiment and embodiment 3 is that no ferric nitrate is added to the configuration of solution A.

[0107] Comparative Example 4

[0108] The difference between this embodiment and embodiment 3 is that in the preparation of solution A, 5.8gNi(NO3)2·6H2O, 11.8gCu(NO3)2·6H2O, 7.2gAl(NO3)3·9H2O, 8.55gZn(NO3)2·6H2O and 4.64gFe(NO3)3 are weighed to prepare solution A of a certain concentration.

[0109] Comparative Example 5

[0110] The difference between this embodiment and embodiment 3 is that the reaction temperature for synthesizing morpholine in this embodiment is 300°C.

[0111] Comparative Example 6

[0112] The difference between this embodiment and embodiment 3 is that the reaction temperature for synthesizing morpholine in this embodiment is 100°C.

[0113] Comparative Example 7

[0114] The difference between this embodiment and embodiment 3 is that the reaction pressure for synthesizing morpholine in this embodiment is 0.1 MPa.

[0115] Comparative Example 8

[0116] The difference between this embodiment and embodiment 3 is that the reaction pressure for synthesizing morpholine in this embodiment is 4.0 MPa.

[0117] Comparative Example 9

[0118] The difference between this embodiment and embodiment 3 is that the diethylene glycol space velocity in the morpholine synthesis reaction of this embodiment is 0.01 L / h.

[0119] Comparative Example 10

[0120] The difference between this embodiment and embodiment 3 is that the diethylene glycol space velocity in the morpholine synthesis reaction of this embodiment is 3 L / h.

[0121] Comparative Example 11

[0122] The difference between this embodiment and embodiment 3 is that the flow rate of crude morpholine in the purification of crude morpholine in the morpholine synthesis reaction in this embodiment is 6800 kg / h.

[0123] Comparative Example 12

[0124] The difference between this embodiment and embodiment 3 is that the flow rate of crude morpholine in the purification of crude morpholine in the morpholine synthesis reaction in this embodiment is 8200 kg / h.

[0125] Comparative Example 13

[0126] The difference between this embodiment and embodiment 3 is that in this embodiment, the crude morpholine coming out of the gas-liquid separator directly enters the subsequent processes such as the deamination tower.

[0127] The yields of morpholine prepared in the above embodiments and comparative examples are shown in Tables 1-3 below.

[0128] Table 1 Preparation parameters of morpholine in each embodiment and comparative example

[0129]

[0130] The molar ratios of the process parameters, active components and additive loading parameters for the catalyst support preparation in Table 1 have been converted according to the masses in the examples.

[0131] Compared with Example 3, we changed the catalyst active component loading parameters, detected the morpholine yield and catalyst activity evaluation in the prepared new morpholine synthesis process, and the specific results are shown in Table 2.

[0132] Table 2

[0133]

[0134] As can be seen from Table 2, by changing the molar ratio of the catalyst active components and the carrier components, comparing the diethylene glycol activity and morpholine selectivity, the optimal molar ratio range of the active component molar ratio Ni(NO3)2:Cu(NO3)2 is 1:(1.24-3.62), and the optimal molar ratio range of the catalyst carrier component molar ratio Al(NO3)3:Zn(NO3)2:Fe(NO3)3 is 1:(0.1-1.5):(0.1-0.5). From the results of the catalyst activity and diethylene glycol selectivity in Comparative Examples 1-4, it can be seen that the activity and selectivity of the catalyst are significantly reduced when the above ranges are exceeded.

[0135] Compared with Example 3, we changed the process parameters for preparing morpholine, and tested the activity and selectivity of the prepared catalyst for synthesizing morpholine from diethylene glycol, as well as the yield of morpholine. The specific results are shown in Table 3 below.

[0136] Table 3

[0137]

[0138] From the above table 3, it can be seen from comparative example 3 and comparative example 13 that there is no synthesis intermediate tank, and the productivity of morpholine obviously decreases. It can be seen from the change of the single factor variable reaction temperature that the temperature exceeds 250 DEG C or is less than 160 DEG C, the catalytic activity of the catalyst decreases obviously, the corresponding diethylene glycol selectivity is also poor, and the final morpholine yield is also low, so in the preparation process of morpholine, the optimum temperature is controlled between 160-250 DEG C. It can be seen from the change of the single factor variable reaction pressure that the reaction pressure exceeds 3.0MPa or is lower than 0.5MPa, the catalytic activity of the catalyst decreases obviously, the corresponding diethylene glycol selectivity is also poor, and the final morpholine yield is also low, so in the preparation process of morpholine, the optimum pressure is controlled between 0.5-3MPa. Changing the single factor variable diethylene glycol space velocity shows that when the diethylene glycol space velocity exceeds 2.5L / h or is lower than 0.1L / h, the catalytic activity of the catalyst decreases significantly, the corresponding diethylene glycol selectivity is also poor, and the final morpholine yield is also low. Therefore, in the process of preparing morpholine, the optimal diethylene glycol space velocity is controlled between 0.1-2.5L / h. Changing the single factor variable crude morpholine flow rate shows that when the crude morpholine flow rate exceeds 8000kg / h or is lower than 7000kg / h, the catalytic activity of the catalyst decreases significantly, the corresponding diethylene glycol selectivity is also poor, and the final morpholine yield is also low. Therefore, in the process of preparing morpholine, the optimal crude morpholine flow rate is controlled between 7000-8000kg / h.

Claims

1. A morpholine synthesis process, characterized in that, The method comprises the following steps: 1) preheated diethylene glycol, ammonia and hydrogen are introduced into a vaporizer, and the vaporized mixed gas enters a reactor, and is catalytically reacted at a temperature of 160-250° C. and a pressure of 0.5-3.0 MPa to generate morpholine; 2) the product of step 1) enters a gas-liquid separator after heat exchange and condensation, and the separated liquid enters a synthesis intermediate tank; 3) the crude morpholine in the synthesis intermediate tank enters a deamination tower for rectification operation; 4) the product after deamination enters a dehydration tower to remove most of water, N-methylmorpholine and N-ethylmorpholine; 5) the product of step 4) enters a lightness removal tower, and enters a product tower after removing a part of water and impurities, and the morpholine product is extracted from the product tower; The catalyst in step 1) is a catalyst with a hydrotalcite-like structure formed by using ZnO / Fe3O4 / γ-Al2O3 as a carrier and loading Ni and Cu active components; wherein the content of each component of the catalyst is 55.8% to 70.2% by weight of ZnO / Fe3O4 / γ-Al2O3, 8% to 15% of Ni, and 20% to 30% of Cu; the catalyst is prepared by the following preparation method: a solution A is prepared according to a molar ratio of Ni(NO3)2·6H2O and Cu(NO3)2·6H2O of 1:(1.24 to 3.62) and a molar ratio of Al(NO3)3·9H2O, Zn(NO3)2·6H2O and Fe(NO3)3 of 1:(0.1 to 1.5):(0.1 to 0.5); and then Na + The concentration of solution B is 2 mol / L, and the molar ratio of Na2CO3 to NaOH is 0.5:1; solution A and solution B are added dropwise to a three-necked flask in a 65°C water bath, and after controlling the pH value to 9-10, they are transferred to a 100 ml hydrothermal kettle, reacted for 6 hours, taken out, washed with water until the pH value is 7, and then placed in a 120°C oven for drying; the dried product is then ground and calcined at 500°C for 3 hours, reduced at 550°C for 3 hours in a mixed gas with a H2 / N2 flow ratio of 1:3, and then cooled to room temperature for passivation to obtain a catalyst; In step 3), the flow rate of the crude morpholine from the synthesis intermediate tank into the deamination tower is controlled at 7000-8000 kg / h.

2. The morpholine synthesis process according to claim 1, wherein In step 1), the molar ratio of diethylene glycol, ammonia and hydrogen is 1:(1-26):(1-10).

3. The morpholine synthesis process according to claim 2, characterized in that: In step 1), the molar ratio of diethylene glycol, ammonia and hydrogen is 1:(1-16):(1-10).

4. The morpholine synthesis process according to claim 1, characterized in that: Most of the gas coming out of the gas-liquid separator in step 2) is recycled, and a small part is discharged as tail gas and recycled after hydrogen extraction.

5. The morpholine synthesis process according to claim 1, characterized in that: The liquid ammonia separated from the deamination tower is returned to the liquid ammonia metering tank for reuse in synthesis, and the high boiling points coming out of the product tower are discharged into the high boiling point tank.

6. The morpholine synthesis process according to claim 1, characterized in that: The impurities described in step 5) include ethylene glycol monomethyl ether.

7. The morpholine synthesis process according to claim 1, characterized in that: The synthesis intermediate tank in step 3) comprises a tank body and a skirt seat (15), wherein the tank body is mounted on the skirt seat (15); a liquid inlet (1) is arranged at the top of the tank body, and a liquid outlet (6) is arranged at the bottom of the tank body, wherein the liquid is discharged through a liquid outlet pipe.

8. The morpholine synthesis process according to claim 7, characterized in that: One end of the liquid outlet pipe is connected to the liquid outlet (6), and the other end is mounted on the side wall of the skirt seat (15) and extends out of the side wall of the skirt seat (15).

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