CN118530194A - Synthesis method of N-ethylpiperazine - Google Patents
Synthesis method of N-ethylpiperazine Download PDFInfo
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- CN118530194A CN118530194A CN202410590188.3A CN202410590188A CN118530194A CN 118530194 A CN118530194 A CN 118530194A CN 202410590188 A CN202410590188 A CN 202410590188A CN 118530194 A CN118530194 A CN 118530194A
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- raney nickel
- ethylpiperazine
- diethanolamine
- synthesizing
- ethylamine
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- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 70
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000007036 catalytic synthesis reaction Methods 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 16
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 16
- 239000007868 Raney catalyst Substances 0.000 claims description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- 238000001994 activation Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 9
- 238000009775 high-speed stirring Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 abstract description 13
- 239000006227 byproduct Substances 0.000 abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D295/03—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 with the ring nitrogen atoms directly attached to acyclic carbon atoms
-
- 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
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of N-ethylpiperazine. According to the invention, ethylamine and diethanolamine are used as raw materials, modified Raney nickel is used as a catalyst, and N-ethylpiperazine is obtained through liquid phase catalytic synthesis reaction. The method can effectively avoid the generation of the by-product N, N-diethyl piperazine in the reaction process, has lower content of other by-products, and improves the yield and selectivity of the N-diethyl piperazine. Meanwhile, the raw material diethanolamine adopted by the invention is prepared by the reaction of ethylene oxide and ammonia, has low raw material cost and wide sources, and is beneficial to promoting the development of the downstream industry of N-ethylpiperazine.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of N-ethylpiperazine.
Background
N-ethylpiperazine is mainly used for synthesizing enfluroxacin, dyes, plant protection agents and the like, has a great deal of application in the polymer industries such as plastics, rubber and the like, can be used as a raw material for preparing medicines for expelling roundworms and firing worms, and has wide application in the production of polymer products such as polyurethane foam plastics, sulfur-containing polyesters, polyoxytetrafluoro ethylene and the like.
At present, the main raw materials for the actual industrial production of N-ethylpiperazine are piperazine and ethanol, but the activity of the ethanol is relatively high, and if the single-pass conversion rate of the piperazine is higher than 40%, the by-product N, N-diethylpiperazine is easy to be produced, so that the production efficiency of the N-ethylpiperazine is influenced. And piperazine is used as a raw material to synthesize the ethylpiperazine, so that the cost of the N-ethylpiperazine is increased, and the development of the downstream industry of the N-ethylpiperazine is not facilitated.
Disclosure of Invention
Aiming at the problems of more byproducts and high cost in the process for producing N-ethylpiperazine in the prior art, the invention provides a synthesis method of N-ethylpiperazine, which adopts diethanolamine and ethylamine as raw materials and modified Raney nickel as a catalyst, so that the generation of the byproducts N, N-diethylpiperazine can be effectively avoided in the reaction process, and the content of other byproducts is lower, thereby improving the yield and selectivity of the N-ethylpiperazine. Meanwhile, the diethanolamine is prepared by the reaction of ethylene oxide and ammonia, has low raw material cost and wide sources, and is beneficial to promoting the development of the downstream industry of N-ethylpiperazine.
In order to achieve the above object, the present invention provides a method for synthesizing N-ethylpiperazine, which uses ethylamine and diethanolamine as raw materials, uses modified raney nickel as a catalyst, and obtains N-ethylpiperazine through a liquid-phase catalytic synthesis reaction;
the preparation method of the modified Raney nickel comprises the following steps:
And soaking Raney nickel in a mixed solution of sodium methoxide, ammonium metavanadate and ethylene glycol for activation, washing and drying, placing the activated Raney nickel at the downstream of the tubular furnace in the gas flow direction, placing sodium hypophosphite at the upstream of the tubular furnace in the gas flow direction, and then sintering at high temperature in a nitrogen atmosphere to obtain the modified Raney nickel catalyst.
Further, the addition ratio of sodium methoxide, ammonium metavanadate and ethylene glycol is 1 mL:0.1-0.15 g:3-5 mL.
Further, the Raney nickel is soaked in a mixed solution of sodium methoxide, ammonium metavanadate and ethylene glycol to be activated for 6 to 8 hours.
Further, the mass ratio of the activated Raney nickel to the sodium hypophosphite is 1:2-3.
Further, the high-temperature sintering temperature is 500-550 ℃, the time is 4-6 h, and the heating rate is 5 ℃/min.
Further, the molar ratio of the ethylamine to the diethanolamine is 1.1 to 2.
Further, the addition amount of the modified Raney nickel is 10 to 15 percent of the mass of the ethylamine and the diethanolamine.
Further, adding ethylamine, diethanolamine and modified Raney nickel into a high-pressure reaction kettle, replacing with nitrogen, replacing oxygen in the high-pressure reaction kettle to ensure that the oxygen content is below 0.01%, replacing a system with hydrogen to ensure that the hydrogen content in the system is above 99.5%, and then increasing the pressure of the reaction kettle to 1-8 MPa with hydrogen to perform liquid-phase catalytic synthesis reaction.
Further, the reaction temperature of the liquid phase catalytic synthesis is 180-210 ℃ and the reaction time is 5-6 h.
Further, the reaction is carried out in a high-pressure reaction kettle with high-speed stirring, and the stirring speed is 400-500 r/min in the reaction process.
The beneficial effects obtained by one or more of the technical schemes of the invention are as follows:
1. According to the synthesis method of N-ethylpiperazine, diethanolamine and ethylamine are adopted as raw materials, and Raney nickel catalyst is further modified, so that the adaptation degree of the catalyst and a raw material system is improved, the generation of byproducts N, N-diethylpiperazine can be effectively avoided in the reaction process, the content of other byproducts is low, and the yield and selectivity of N-ethylpiperazine are improved.
2. The raw material diethanolamine adopted by the invention is prepared by the reaction of ethylene oxide and ammonia, has low raw material cost and wide sources, and is beneficial to promoting the development of the downstream industry of N-ethylpiperazine.
Detailed Description
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
The embodiment provides a synthesis method of N-ethylpiperazine, which comprises the following specific preparation steps:
(1) Preparing modified Raney nickel: and (3) immersing the Raney nickel in a mixed solution of 10mL of sodium methoxide, 1g of ammonium metavanadate and 30mL of ethylene glycol for activation for 6 hours, washing and drying, placing the activated Raney nickel at the downstream of the gas flow direction of a tubular furnace, placing sodium hypophosphite (the mass ratio of the activated Raney nickel to the sodium hypophosphite is 1:2) at the upstream of the gas flow direction of the tubular furnace, and then sintering at 500 ℃ for 6 hours under a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, so as to obtain the modified Raney nickel catalyst.
(2) Adding ethylamine, diethanolamine and modified Raney nickel into a high-pressure reaction kettle with high-speed stirring (the molar ratio of the ethylamine to the diethanolamine is 1.1, the addition amount of the modified Raney nickel is 10% of the mass of the ethylamine and the diethanolamine), replacing by nitrogen, replacing oxygen in the high-pressure reaction kettle, ensuring that the oxygen content is below 0.01%, replacing a system by hydrogen, ensuring that the hydrogen content in the system is above 99.5%, adding hydrogen to the pressure of the reaction kettle to 1MPa, setting the stirring rotating speed to 500r/min, and carrying out liquid-phase catalytic synthesis reaction at the reaction temperature of 180 ℃ for 6h.
Example 2
The embodiment provides a synthesis method of N-ethylpiperazine, which comprises the following specific preparation steps:
(1) Preparing modified Raney nickel: and (3) immersing the Raney nickel in a mixed solution of 10mL of sodium methoxide, 1.5g of ammonium metavanadate and 30mL of ethylene glycol for activation for 6 hours, washing and drying, placing the activated Raney nickel at the downstream of the gas flow direction of a tubular furnace, placing sodium hypophosphite at the upstream of the gas flow direction of the tubular furnace (the mass ratio of the activated Raney nickel to the sodium hypophosphite is 1:2), and then sintering at 550 ℃ for 4 hours under a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, so as to obtain the modified Raney nickel catalyst.
(2) Adding ethylamine, diethanolamine and modified Raney nickel into a high-pressure reaction kettle with high-speed stirring (the molar ratio of the ethylamine to the diethanolamine is 1.5, the addition amount of the modified Raney nickel is 10% of the mass of the ethylamine and the diethanolamine), replacing by nitrogen, replacing oxygen in the high-pressure reaction kettle, ensuring that the oxygen content is below 0.01%, replacing a system by hydrogen, ensuring that the hydrogen content in the system is above 99.5%, adding hydrogen to the pressure of the reaction kettle to 4MPa, setting the stirring rotating speed to 400r/min, and carrying out liquid-phase catalytic synthesis reaction at the reaction temperature of 210 ℃ for 5h.
Example 3
The embodiment provides a synthesis method of N-ethylpiperazine, which comprises the following specific preparation steps:
(1) Preparing modified Raney nickel: and (3) immersing the Raney nickel in a mixed solution of 10mL of sodium methoxide, 1.5g of ammonium metavanadate and 50mL of ethylene glycol for activation for 8 hours, washing and drying, placing the activated Raney nickel at the downstream of the gas flow direction of a tubular furnace, placing sodium hypophosphite at the upstream of the gas flow direction of the tubular furnace (the mass ratio of the activated Raney nickel to the sodium hypophosphite is 1:3), and then sintering at a high temperature of 500 ℃ for 5 hours under a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, so as to obtain the modified Raney nickel catalyst.
(2) Adding ethylamine, diethanolamine and modified Raney nickel into a high-pressure reaction kettle with high-speed stirring (the molar ratio of the ethylamine to the diethanolamine is 2, the addition amount of the modified Raney nickel is 15% of the mass of the ethylamine and the diethanolamine), replacing by nitrogen, replacing oxygen in the high-pressure reaction kettle, ensuring the oxygen content to be below 0.01%, replacing a system by hydrogen, ensuring the hydrogen content in the system to be above 99.5%, adding hydrogen to the pressure of the reaction kettle to 8MPa, setting the stirring rotating speed to be 500r/min, and carrying out liquid-phase catalytic synthesis reaction at the reaction temperature of 200 ℃ for 5h.
Example 4
The embodiment provides a synthesis method of N-ethylpiperazine, which comprises the following specific preparation steps:
(1) Preparing modified Raney nickel: and (3) immersing the Raney nickel in a mixed solution of 10mL of sodium methoxide, 1.5g of ammonium metavanadate and 30mL of ethylene glycol for activation for 8 hours, washing and drying, placing the activated Raney nickel at the downstream of the gas flow direction of a tubular furnace, placing sodium hypophosphite at the upstream of the gas flow direction of the tubular furnace (the mass ratio of the activated Raney nickel to the sodium hypophosphite is 1:2.5), and then sintering at 550 ℃ for 6 hours under a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, so as to obtain the modified Raney nickel catalyst.
(2) Adding ethylamine, diethanolamine and modified Raney nickel into a high-pressure reaction kettle with high-speed stirring (the molar ratio of the ethylamine to the diethanolamine is 1.8, the addition amount of the modified Raney nickel is 12% of the mass of the ethylamine and the diethanolamine), replacing by nitrogen, replacing oxygen in the high-pressure reaction kettle, ensuring that the oxygen content is below 0.01%, replacing a system by hydrogen, ensuring that the hydrogen content in the system is above 99.5%, adding hydrogen to the pressure of the reaction kettle to 6MPa, setting the stirring rotating speed to 500r/min, and carrying out liquid-phase catalytic synthesis reaction at the reaction temperature of 210 ℃ for 5h.
Example 5
The embodiment provides a synthesis method of N-ethylpiperazine, which comprises the following specific preparation steps:
(1) Preparing modified Raney nickel: and (3) immersing the Raney nickel in a mixed solution of 10mL of sodium methoxide, 1g of ammonium metavanadate and 30mL of ethylene glycol for activation for 6 hours, washing and drying, placing the activated Raney nickel at the downstream of the gas flow direction of a tubular furnace, placing sodium hypophosphite (the mass ratio of the activated Raney nickel to the sodium hypophosphite is 1:2) at the upstream of the gas flow direction of the tubular furnace, and then sintering at 550 ℃ for 4 hours under a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, so as to obtain the modified Raney nickel catalyst.
(2) Adding ethylamine, diethanolamine and modified Raney nickel into a high-pressure reaction kettle with high-speed stirring (the molar ratio of the ethylamine to the diethanolamine is 1.5, the addition amount of the modified Raney nickel is 15% of the mass of the ethylamine and the diethanolamine), replacing by nitrogen, replacing oxygen in the high-pressure reaction kettle, ensuring that the oxygen content is below 0.01%, replacing a system by hydrogen, ensuring that the hydrogen content in the system is above 99.5%, adding hydrogen to 5MPa, setting the stirring rotating speed to 500r/min, and carrying out liquid-phase catalytic synthesis reaction at the reaction temperature of 180 ℃ for 6h.
Comparative example 1
The comparative example provides a synthesis method of N-ethylpiperazine, which comprises the following specific preparation steps:
Adding ethylamine, diethanolamine and Raney nickel into a high-pressure reaction kettle with high-speed stirring (the molar ratio of the ethylamine to the diethanolamine is 1.1, the addition amount of the Raney nickel is 10% of the mass of the ethylamine and the diethanolamine), replacing by nitrogen, replacing oxygen in the high-pressure reaction kettle, ensuring that the oxygen content is below 0.01%, replacing a system by hydrogen, ensuring that the hydrogen content in the system is above 99.5%, adding hydrogen to the pressure of the reaction kettle to 1MPa, setting the stirring rotating speed to 500r/min, and carrying out liquid-phase catalytic synthesis reaction at 180 ℃ for 6h.
Comparative example 2
The comparative example provides a synthesis method of N-ethylpiperazine, which comprises the following specific preparation steps:
(1) Preparing modified Raney nickel: and (3) placing Raney nickel at the downstream of the gas flow direction of the tubular furnace, placing sodium hypophosphite (the mass ratio of Raney nickel to sodium hypophosphite is 1:2) at the upstream of the gas flow direction of the tubular furnace, and then sintering at 500 ℃ for 6 hours under the nitrogen atmosphere, wherein the heating rate is 5 ℃/min, so as to obtain the modified Raney nickel catalyst.
(2) Adding ethylamine, diethanolamine and modified Raney nickel into a high-pressure reaction kettle with high-speed stirring (the molar ratio of the ethylamine to the diethanolamine is 1.1, the addition amount of the modified Raney nickel is 10% of the mass of the ethylamine and the diethanolamine), replacing by nitrogen, replacing oxygen in the high-pressure reaction kettle, ensuring that the oxygen content is below 0.01%, replacing a system by hydrogen, ensuring that the hydrogen content in the system is above 99.5%, adding hydrogen to the pressure of the reaction kettle to 1MPa, setting the stirring rotating speed to 500r/min, and carrying out liquid-phase catalytic synthesis reaction at the reaction temperature of 180 ℃ for 6h.
The reacted materials in examples 1 to 5 and comparative examples 1 and 2 were subjected to chromatographic analysis, and table 1 shows the contents of diethylamine, piperazine, N-ethylpiperazine, ethylamine and diethanolamine in the reacted materials (except for water), and the other impurities were not more than 0.1%.
TABLE 1
| Sample of | Ethylamine (%) | Diethylamine (%) | Piperazine (%) | N-ethylpiperazine (%) | Diethanolamine (%) |
| Example 1 | 1.25 | 2.77 | 2.37 | 90.52 | 3.07 |
| Example 2 | 1.17 | 2.48 | 2.15 | 91.47 | 2.68 |
| Example 3 | 1.69 | 3.05 | 2.41 | 89.61 | 3.16 |
| Example 4 | 1.26 | 2.55 | 2.19 | 90.94 | 3.02 |
| Example 5 | 1.18 | 2.50 | 2.25 | 91.23 | 2.77 |
| Comparative example 1 | 4.74 | 5.51 | 4.83 | 78.91 | 5.95 |
| Comparative example 2 | 2.66 | 4.19 | 3.12 | 85.63 | 4.31 |
As can be seen from Table 1, the synthesis method of N-ethylpiperazine provided by the invention has the advantages of higher yield, excellent selectivity and lower byproduct occupation. The excellent effect achieved by the invention is derived from the selection of reactants, and diethanolamine and ethylamine are adopted as raw materials, so that the generation of a byproduct N, N-diethyl piperazine can be avoided; on the other hand, due to the modification of the Raney nickel catalyst, the catalytic activity can be obviously enhanced, the content of other byproducts can be reduced, and the selectivity of the N-ethylpiperazine can be improved by carrying out the process of synergistic activation of Raney nickel in sodium methoxide, ammonium metavanadate and glycol solution and then high-temperature phosphating.
Claims (10)
1. A synthesis method of N-ethylpiperazine is characterized by comprising the following steps:
using ethylamine and diethanolamine as raw materials, using modified Raney nickel as a catalyst, and obtaining N-ethylpiperazine through liquid phase catalytic synthesis reaction;
the preparation method of the modified Raney nickel comprises the following steps:
And soaking Raney nickel in a mixed solution of sodium methoxide, ammonium metavanadate and ethylene glycol for activation, washing and drying, placing the activated Raney nickel at the downstream of the tubular furnace in the gas flow direction, placing sodium hypophosphite at the upstream of the tubular furnace in the gas flow direction, and then sintering at high temperature in a nitrogen atmosphere to obtain the modified Raney nickel catalyst.
2. The method for synthesizing the N-ethylpiperazine according to claim 1, wherein: the addition ratio of the sodium methoxide to the ammonium metavanadate to the glycol is 1mL, 0.1-0.15 g and 3-5 mL.
3. The method for synthesizing the N-ethylpiperazine according to claim 1, wherein: and immersing Raney nickel in a mixed solution of sodium methoxide, ammonium metavanadate and ethylene glycol for activation for 6-8 h.
4. The method for synthesizing the N-ethylpiperazine according to claim 1, wherein: the mass ratio of the activated Raney nickel to the sodium hypophosphite is 1:2-3.
5. The method for synthesizing the N-ethylpiperazine according to claim 1, wherein: the high-temperature sintering temperature is 500-550 ℃, the time is 4-6 h, and the heating rate is 5 ℃/min.
6. The method for synthesizing the N-ethylpiperazine according to claim 1, wherein: the mol ratio of the ethylamine to the diethanolamine is 1.1-2.
7. The method for synthesizing the N-ethylpiperazine according to claim 1, wherein: the addition amount of the modified Raney nickel is 10-15% of the mass of the ethylamine and the diethanolamine.
8. The method for synthesizing the N-ethylpiperazine according to claim 1, wherein: adding ethylamine, diethanolamine and modified Raney nickel into a high-pressure reaction kettle, replacing with nitrogen, replacing oxygen in the high-pressure reaction kettle to ensure that the oxygen content is below 0.01%, replacing a system with hydrogen to ensure that the hydrogen content in the system is above 99.5%, and then adding hydrogen to the pressure of the reaction kettle to 1-8 MPa to perform liquid-phase catalytic synthesis reaction.
9. The method for synthesizing the N-ethylpiperazine according to claim 8, wherein: the liquid phase catalytic synthesis reaction temperature is 180-210 ℃ and the reaction time is 5-6 h.
10. The method for synthesizing the N-ethylpiperazine according to claim 8, wherein: the reaction is carried out in a high-pressure reaction kettle with high-speed stirring, and the stirring speed is 400-500 r/min in the reaction process.
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