CN110563669A - Method and device for improving morpholine purity - Google Patents
Method and device for improving morpholine purity Download PDFInfo
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- CN110563669A CN110563669A CN201910955719.3A CN201910955719A CN110563669A CN 110563669 A CN110563669 A CN 110563669A CN 201910955719 A CN201910955719 A CN 201910955719A CN 110563669 A CN110563669 A CN 110563669A
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 61
- 238000000605 extraction Methods 0.000 claims abstract description 60
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims abstract description 57
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims abstract description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000010409 thin film Substances 0.000 claims abstract description 25
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 230000008020 evaporation Effects 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000012535 impurity Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 16
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 9
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical group CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 4
- WAZPLXZGZWWXDQ-UHFFFAOYSA-N 4-methyl-4-oxidomorpholin-4-ium;hydrate Chemical compound O.C[N+]1([O-])CCOCC1 WAZPLXZGZWWXDQ-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 19
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- 238000005265 energy consumption Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007790 scraping Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000010006 flight Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229960005181 morphine Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/22—Evaporating by bringing a thin layer of the liquid into contact with a heated surface
- B01D1/222—In rotating vessels; vessels with movable parts
- B01D1/223—In rotating vessels; vessels with movable parts containing a rotor
- B01D1/225—In rotating vessels; vessels with movable parts containing a rotor with blades or scrapers
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
the invention discloses a method for improving morpholine purity, which comprises the steps of dropwise adding hydrogen peroxide into a morpholine aqueous solution at normal temperature to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture; after the reaction is finished, carrying out micro-heating on the obtained first mixture of the product, separating out crystals, and filtering to obtain a second mixture; adding solid sodium hydroxide into the obtained second mixture, filtering, feeding into a first rectifying tower, and condensing and collecting the tower top to obtain a first distillate; introducing the obtained first distillate into an extraction tower, adding an extracting agent into the extraction tower to obtain an extraction phase, adding the extraction phase into a second rectification tower, condensing and collecting the top of the tower to obtain a second distillate, wherein the main components of the second distillate are morpholine and N-ethyl morpholine; and adding the second distillate into a thin film evaporator for rectification, wherein the evaporation temperature is 128-132 ℃, the evaporant is condensed by a condenser to obtain morpholine, and the substance obtained in the evaporator is N-ethylmorpholine.
Description
Technical Field
the invention relates to the technical field of chemical technology, in particular to a method and a device for improving morpholine purity.
Background
Morpholine, also known as morphine, has the molecular formulaC4H9NO, or written as O (CH)2CH2)2and (4) NH. At normal temperature, morpholine is a colorless oily liquid, and has the properties of nitrogen and oxygen heterocycles, so that morpholine occupies an important position in chemical production, is an intermediate for manufacturing various fine chemical products, and has wide application in the fields of rubber, medicines, pesticides, coatings and the like.
at present, a diethylene glycol catalytic aminolysis cyclization method is mainly adopted for industrially preparing morpholine, and the synthesis process can be mainly divided into 3 types according to different reaction pressures, wherein the (1) high-pressure liquid phase method; low pressure vapor-liquid phase contact process; the (3) low-pressure vapor phase method. Most commonly, a low-pressure vapor phase method is adopted for preparing the catalyst, and the method has the advantages of simple process, high conversion rate, sufficient raw material source, small equipment investment and the like, and is widely popularized and used.
the morpholine process flow comprises the following steps: diethylene glycol and ammonia are synthesized into morpholine in a fixed bed adiabatic reactor according to a certain proportion under the conditions of a catalyst and hydrogen, the synthesis gas is separated by condensation, gas-phase hydrogen is recycled, a liquid phase is continuously separated from ammonia gas by a dehydrogenation tower for recycling, and a morpholine aqueous solution is finally obtained by a product tower from a kettle solution.
disclosure of Invention
The invention provides a method for improving morpholine purity, which is used for solving the technical problems of higher purification energy consumption and lower conversion rate of crude morpholine in the prior art.
the first purpose of the invention is to provide a method for improving the purity of morpholine, which comprises the following steps:
s1: at normal temperature, the morpholine aqueous solution is in pure CO2Dropwise adding hydrogen peroxide under the atmosphere and the pH of 7-9, and reacting for 5-6 hours to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture; the first mixture is composed of morpholine, N-methylmorpholine oxide and N-ethylmorpholineWater and impurities;
S2: after the reaction of step S1, the obtained first mixture of products is heated slightly to precipitate crystals, and filtered to obtain a second mixture; the second mixture consists of morpholine, N-ethyl morpholine, water and impurities;
S3: adding solid sodium hydroxide into the obtained second mixture, filtering, and then sending into a first rectifying tower, wherein the operating pressure of the first rectifying tower is 90-100 kpa, and the tower top temperature is 135-138 ℃; the temperature of the tower bottom is 150-155 ℃, and a first distillate is obtained by condensing and collecting the tower top; the first distillate consists of morpholine, N-ethyl morpholine, a small amount of water and impurities;
S4: introducing the first distillate obtained in the step S3 into an extraction tower, adding an extracting agent into the extraction tower to obtain an extraction phase, adding the extraction phase into a second rectifying tower for recovering the extracting agent, wherein the operating pressure of the second rectifying tower is 100-105 kpa, and the tower top temperature is 130-140 ℃; the temperature of the tower bottom is 155-160 ℃, the tower top is condensed and collected to obtain a second distillate, and the main components of the second distillate are morpholine and N-ethylmorpholine;
S5: and adding the second distillate into a thin film evaporator for rectification, wherein the evaporation temperature is 128-135 ℃, the evaporant is condensed by a condenser to obtain morpholine, and the substance obtained in the evaporator is N-ethylmorpholine.
In order to better implement the present invention, the crystals precipitated in step S2 are recrystallized from acetone to obtain N-methylmorpholine oxide hydrate.
in order to better implement the invention, further, the process parameters of the evaporation film device during operation are as follows: the number of the scrapers is 4; the vacuum degree is 70-90 kpa.
The working principle is as follows: the invention provides a preparation method for improving morpholine purity, wherein a morpholine crude product obtained in a morpholine preparation process is a morpholine aqueous solution containing 55-56% of morpholine, 20-22% of N-methylmorpholine, 20-22% of N-ethylmorpholine, 1-5% of other impurities and water; the existing purification of morpholine aqueous solution adopts a four-tower rectification mode, the purification mode is single, and the purification process needs to consume more energy to reach the purification concentration, so that the cost waste and the environmental pollution are great. The scheme is provided for achieving the purposes of energy conservation and environmental protection.
The purification method provided by the invention is to firstly put the morpholine aqueous solution in pure CO2under the condition that the PH value is 7-9, preferably 8, hydrogen peroxide is dripped, so that N-methylmorpholine in the morpholine crude product aqueous solution is oxidized into N-methylmorpholine oxide, the reason for the operation is that the boiling points of morpholine, N-methylmorpholine and N-ethylmorpholine in the morpholine aqueous solution are close to each other, the rectification based on the boiling point principle in the prior art is the main reason for larger energy consumption, in order to save energy consumption, N-methylmorpholine is converted into N-methylmorpholine oxide, and after reaction, the N-methylmorpholine oxide is subjected to micro-heating treatment, the micro-heating step can not only remove redundant hydrogen peroxide in the morpholine aqueous solution, but also crystallize the N-methyl morpholine oxide just converted in the morpholine aqueous solution, and at the moment, the N-methyl morpholine in the original morpholine aqueous solution can be removed by filtering the morpholine aqueous solution. The steps of rectification are reduced, thereby achieving the purpose of saving energy consumption.
The N-methylmorpholine oxide obtained by crystallization is recrystallized by acetone to obtain N-methylmorpholine oxide hydrate, and the N-methylmorpholine oxide is a special excellent solvent with extremely strong solubility to cellulose and can be used for spinning, manufacturing artificial cotton, cellophane and the like.
the second mixture for removing the N-methylmorpholine mainly comprises morpholine, N-ethylmorpholine, water and other impurities, and in order to achieve the purpose of removing the N-ethylmorpholine, the water and the impurities, the second mixture is dehydrated first. The dehydration is carried out by adding sodium hydroxide, filtering and then sending into a first rectifying tower for rectification, wherein the operating pressure of the first rectifying tower is 90-100 kpa, and the temperature of the tower top is 135-138 ℃; the temperature of the tower bottom is 150-155 ℃; the reflux ratio is 5-7, the number of theoretical plates is more than 30, the first distillate is obtained by distilling the first distillation column top and condensing the first distillate by a condenser, the first distillate mainly comprises morpholine, N-ethyl morpholine, a small amount of water and impurities, and the distillation efficiency can be improved by the operation parameters;
Adding the first distillate into an extraction tower, wherein the operating pressure of the extraction tower is 100-105 kpa in absolute pressure, the extraction temperature is 80-90 ℃, extracting an extract phase after extraction, forming an extract raffinate phase by impurities and water which are insoluble in an extractant and discharging, outputting the extract phase from the top of the extraction tower, transferring the extract phase into a second rectifying tower for recovering the extractant, wherein the operating pressure of the second rectifying tower is 100-105 kpa, and the temperature of the top of the tower is 130-140 ℃; and the tower bottom temperature is 155-160 ℃, the reflux ratio is 5-7, the number of theoretical plates is more than 30, and a second distillate is collected at the tower top of the second rectification, wherein the second distillate mainly comprises morpholine and N-ethylmorpholine.
and (3) introducing the second distillate into a thin film evaporator for rectification, wherein the residence time of liquid in the thin film evaporator is as follows: 20-200 s, working temperature of 139-145 ℃, vacuum degree of 70-90 kpa, the number of scrapers of 4, scraper rotation speed of 200-500 r/min, and separating N-ethylmorpholine and morpholine through the difference of boiling points, wherein the boiling point of morpholine is as follows: 128.3 ℃, the boiling point of N-methylmorpholine is 115.4 ℃, the boiling point of N-ethylmorpholine is 138 ℃, the boiling point of morpholine is between N-methylmorpholine and N-ethylmorpholine, when purification is carried out through rectification, part of morpholine can be transferred into N-methylmorpholine and N-ethylmorpholine all the time, and therefore the purity of purification is affected.
The extracting agent is preferably N-heptanol, sec-octanol or N-octanol, and the solvent can be mutually soluble with morpholine and N-ethyl morpholine and almost insoluble with water, so that morpholine and N-ethyl morpholine are dissolved by extraction action, and separated from water, and then morpholine and N-ethyl morpholine are separated by means of difference of boiling points.
the purification method has the advantages of easy operation in the preparation process, high purification efficiency, low energy consumption and capability of effectively purifying morpholine and achieving the purposes of energy conservation and environmental protection.
the second purpose of the invention is to provide a device for improving the purity of morpholine, which comprises a reactor, a first rectifying tower, an extraction tower, a second rectifying tower and a thin film evaporator which are connected in sequence;
The reactor is provided with a connecting pipe connected with a first rectifying tower, the top of the first rectifying tower is provided with a first exhaust pipe, and the free end of the first exhaust pipe is connected with a first condenser; a first discharge pipe of the first condenser is connected with the extraction tower, an extraction discharge pipe is arranged at the top of the extraction tower and connected with the second rectification tower, a second exhaust pipe is arranged at the top of the second rectification tower, and the free end of the second exhaust pipe is connected with a second condenser; the second condenser is provided with a second discharge pipe, and the second discharge pipe is connected with the thin film evaporator.
In order to better realize the invention, the thin film evaporator comprises an evaporator and a third condenser, the evaporator comprises a shell, a heating shell for introducing steam is arranged on the outer wall of the shell, a rotating shaft is arranged in the shell, a scraper component is arranged on the rotating shaft, the scraper component comprises a rotor connected with the rotating shaft, the rotor is an eccentric wheel, and a first scraper and a second scraper are arranged on two sides of the rotor.
In order to better implement the invention, the number of the scraper components on the rotating shaft is two, and the two scraper components are arranged up and down.
the working principle is as follows:
In the process of purifying morpholine, a specially-made device is adopted to greatly influence the purification efficiency, and the device comprises a reactor, a first rectifying tower, an extraction tower, a second rectifying tower and a film evaporator. In order to save energy consumption, the thin film evaporator is improved, the thin film evaporator mainly comprises an evaporator and a third condenser, in the process of thin film evaporation, the influence of the gap between a scraper component and the inner wall of a shell on evaporation efficiency is large, after a second distillate is injected into the evaporator, the evaporator starts to work, the distillate is rapidly evaporated and rectified under the action of a scraper, in order to improve efficiency and be more suitable for fluid circulation, a rotor of the scraper component is arranged as an eccentric wheel, so that rotating traces of the scraper are not uniform through the arrangement of the eccentric wheel, the efficiency is low when the distance between the scraper and the shell is too small or too large, the gap is smaller and more flexible through the arrangement of the eccentric rotor, two scraper components are arranged up and down, and the gap in the whole is more reasonable, higher evaporation efficiency is achieved.
The embodiment of the invention has the beneficial effects that: according to the invention, N-methylmorpholine in the morpholine aqueous solution is converted, so that the energy consumption loss in the rectification process is reduced, and impurities and water are removed by carrying out processes such as dehydration, extraction and the like on the second mixture, so that the purposes of reducing energy consumption and improving the morpholine purity are achieved;
The invention improves the influence of the constant distance between the scraper and the inner wall of the shell on the evaporation efficiency by improving the scraper component in the evaporator, thereby achieving the purpose of improving the evaporation efficiency and further achieving the purposes of energy conservation and environmental protection.
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 structural diagram of an apparatus for improving morpholine purity according to the present invention;
FIG. 2 is a schematic view of the evaporator according to the present invention;
Icon: 100-reactor, 110-connecting pipe, 200-first rectifying tower, 210-first exhaust pipe, 220-first condenser, 230-first discharge pipe, 300-extracting tower, 310-extracting discharge pipe, 400-second rectifying tower, 410-second exhaust pipe, 420-second condenser, 430-second discharge pipe, 510-evaporator, 511-shell, 512-heating shell, 513-rotating shaft, 514-rotor, 515-first scraper, 516-second scraper, 520-third condenser.
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 with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
example 1:
A method for improving the purity of morpholine comprises the following steps: .
S1: at normal temperature, an aqueous morpholine solution is placed in a reactor 100 under the following reaction conditions: CO 22dropwise adding hydrogen peroxide under the atmosphere and the pH of 7, and reacting for 5 hours to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture;
The first mixture consists of morpholine, N-methylmorpholine oxide, N-ethylmorpholine, water and impurities;
s2: after the reaction of step S1, the obtained first mixture of products is heated slightly in the reactor 100 to precipitate crystals, and then filtered to obtain a second mixture;
the second mixture consists of morpholine, N-ethyl morpholine, water and impurities;
S3: adding solid sodium hydroxide into the obtained second mixture in a reactor 100, filtering, and then sending the second mixture into a first rectifying tower 200 through a connecting pipe 110, wherein the operating pressure of the first rectifying tower 200 is 90kpa, and the tower top temperature is 135 ℃; the temperature of the tower bottom is 150 ℃, the tower top is conveyed to a first condenser 220 through a first exhaust pipe 210 for condensation and collection to obtain a first distillate, and the first distillate is discharged through a first exhaust pipe 230;
the first distillate consists of morpholine, N-ethyl morpholine, a small amount of water and impurities;
S4: introducing the first distillate obtained in the step S3 into an extraction tower 300, adding n-heptanol into the extraction tower 300 to obtain an extract phase, and sending the extract phase into a second rectifying tower 400 through an extraction discharge pipe 310 for rectification, wherein the operating pressure of the second rectifying tower 400 is 100kpa, and the tower top temperature is 130 ℃; the temperature of the tower bottom is 155 ℃, the tower top of the second rectifying tower 400 is connected with a second condenser 420 through a second exhaust pipe 410, condensation and collection are carried out to obtain a second distillate, and the process parameters of the extraction tower 300 are as follows: the operation pressure is 100kpa, the extraction temperature is 80 DEG C
the main components of the second distillate are morpholine and N-ethylmorpholine;
S5: the second distillate is sent to a thin film evaporator through a second discharge pipe 430 for rectification, the thin film evaporator comprises an evaporator 510 and a third condenser 520, in the evaporator 510, the evaporation temperature is 128 ℃, the vacuum degree is 70kpa, the evaporant is condensed through the third condenser 520 to obtain morpholine, N-ethyl morpholine is contained in the evaporator 510, and the purity of the morpholine is 99.7%.
The evaporator 510 structurally comprises a shell 511, wherein a heating shell 512 for introducing steam is arranged on the outer wall of the shell 511, a rotating shaft 513 is arranged in the shell 511, a scraping plate assembly is arranged on the rotating shaft 513, the scraping plate assembly comprises a rotor 514 connected with the rotating shaft 513, the rotor 514 is an eccentric wheel, and a first scraping blade 515 and a second scraping blade 516 are arranged on two sides of the rotor 514; two scraper assemblies are arranged on the rotating shaft 513, and the two scraper assemblies are arranged up and down; preferably 4 flights.
Example 2:
a method for improving the purity of morpholine comprises the following steps: .
s1: at normal temperature, an aqueous morpholine solution is placed in a reactor 100 under the following reaction conditions: CO 22dropwise adding hydrogen peroxide under the atmosphere and the pH of 8, and reacting for 5.5 hours to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture;
the first mixture consists of morpholine, N-methylmorpholine oxide, N-ethylmorpholine, water and impurities;
S2: after the reaction of step S1, the obtained first mixture of products is heated slightly in the reactor 100 to precipitate crystals, and then filtered to obtain a second mixture;
The second mixture consists of morpholine, N-ethyl morpholine, water and impurities;
S3: adding solid sodium hydroxide into the obtained second mixture in a reactor 100, filtering, and then feeding the second mixture into a first rectifying tower 200 through a connecting pipe 110, wherein the operating pressure of the first rectifying tower 200 is 92kpa, and the tower top temperature is 136 ℃; the temperature of the tower bottom is 151 ℃, the tower top is conveyed to a first condenser 220 through a first exhaust pipe 210 for condensation and collection to obtain a first distillate, and the first distillate is discharged through a first exhaust pipe 230;
the first distillate consists of morpholine, N-ethyl morpholine, a small amount of water and impurities;
s4: introducing the first distillate obtained in the step S3 into an extraction tower 300, adding octanol into the extraction tower 300 to obtain an extract phase, and sending the extract phase into a second rectifying tower 400 through an extraction discharge pipe 310 for rectification, wherein the operating pressure of the second rectifying tower 400 is 102kpa, and the tower top temperature is 132 ℃; the temperature of the tower bottom is 156 ℃, the tower top of the second rectifying tower 400 is connected with a second condenser 420 through a second exhaust pipe 410, and a second distillate is obtained by condensation and collection, wherein the process parameters of the extraction tower 300 are as follows: the operating pressure is 103kpa, and the extraction temperature is 85 ℃;
The main components of the second distillate are morpholine and N-ethylmorpholine;
S5: the second distillate is sent to a thin film evaporator through a second discharge pipe 430 for rectification, the thin film evaporator comprises an evaporator 510 and a third condenser 520, in the evaporator 510, the evaporation temperature is 129 ℃, the vacuum degree is 80kpa, the evaporant is condensed through the third condenser 520 to obtain morpholine, N-ethyl morpholine is contained in the evaporator 510, and the purity of the morpholine is 99.8%.
The evaporator 510 has the same structure as that of embodiment 1.
example 3:
a method for improving the purity of morpholine comprises the following steps: .
S1: at normal temperature, an aqueous morpholine solution is placed in a reactor 100 under the following reaction conditions: CO 22Dropwise adding hydrogen peroxide under the atmosphere and the pH of 8, and reacting for 5.5 hours to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture;
The first mixture consists of morpholine, N-methylmorpholine oxide, N-ethylmorpholine, water and impurities;
s2: after the reaction of step S1, the obtained first mixture of products is heated slightly in the reactor 100 to precipitate crystals, and then filtered to obtain a second mixture;
the second mixture consists of morpholine, N-ethyl morpholine, water and impurities;
S3: adding solid sodium hydroxide into the obtained second mixture in a reactor 100, filtering, and then sending the second mixture into a first rectifying tower 200 through a connecting pipe 110, wherein the operating pressure of the first rectifying tower 200 is 95kpa, and the tower top temperature is 137 ℃; the temperature of the tower bottom is 153 ℃, the tower top is conveyed to a first condenser 220 through a first exhaust pipe 210 for condensation and collection to obtain a first distillate, and the first distillate is discharged through a first exhaust pipe 230;
the first distillate consists of morpholine, N-ethyl morpholine, a small amount of water and impurities;
S4: introducing the first distillate obtained in the step S3 into an extraction tower 300, adding n-octanol into the extraction tower 300 to obtain an extract phase, and sending the extract phase into a second rectifying tower 400 through an extraction discharge pipe 310 for rectification, wherein the operating pressure of the second rectifying tower 400 is 103kpa, and the tower top temperature is 135 ℃; the temperature of the tower bottom is 157 ℃, the tower top of the second rectifying tower 400 is connected with a second condenser 420 through a second exhaust pipe 410, and the second distillate is obtained by condensation and collection, wherein the process parameters of the extraction tower 300 are as follows: the operating pressure is 104kpa, and the extraction temperature is 88 ℃;
The main components of the second distillate are morpholine and N-ethylmorpholine;
S5: the second distillate is sent to a thin film evaporator through a second discharge pipe 430 for rectification, the thin film evaporator comprises an evaporator 510 and a third condenser 520, in the evaporator 510, the evaporation temperature is 130 ℃, the vacuum degree is 86kpa, the evaporant is condensed through the third condenser 520 to obtain morpholine, N-ethyl morpholine is contained in the evaporator 510, and the purity of the morpholine is 99.8%.
the evaporator 510 has the same structure as that of embodiment 1.
example 4:
a method for improving the purity of morpholine comprises the following steps: .
s1: at normal temperature, an aqueous morpholine solution is placed in a reactor 100 under the following reaction conditions: CO 22dropwise adding hydrogen peroxide under the atmosphere and the pH of 8, and reacting for 5.7 hours to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture;
the first mixture consists of morpholine, N-methylmorpholine oxide, N-ethylmorpholine, water and impurities;
s2: after the reaction of step S1, the obtained first mixture of products is heated slightly in the reactor 100 to precipitate crystals, and then filtered to obtain a second mixture;
The second mixture consists of morpholine, N-ethyl morpholine, water and impurities;
s3: adding solid sodium hydroxide into the obtained second mixture in a reactor 100, filtering, and then sending the second mixture into a first rectifying tower 200 through a connecting pipe 110, wherein the operating pressure of the first rectifying tower 200 is 98kpa, and the tower top temperature is 137 ℃; the temperature of the tower bottom is 154 ℃, the tower top is conveyed to a first condenser 220 through a first exhaust pipe 210 for condensation and collection to obtain a first distillate, and the first distillate is discharged through a first exhaust pipe 230;
The first distillate consists of morpholine, N-ethyl morpholine, a small amount of water and impurities;
S4: introducing the first distillate obtained in the step S3 into an extraction tower 300, adding n-heptanol into the extraction tower 300 to obtain an extract phase, and sending the extract phase into a second rectifying tower 400 through an extraction discharge pipe 310 for rectification, wherein the operating pressure of the second rectifying tower 400 is 104kpa, and the tower top temperature is 138 ℃; the temperature of the tower bottom is 158 ℃, the tower top of the second rectifying tower 400 is connected with a second condenser 420 through a second exhaust pipe 410, and the second distillate is obtained by condensation and collection, wherein the process parameters of the extraction tower 300 are as follows: the operating pressure is 104kpa, and the extraction temperature is 85 ℃;
The main components of the second distillate are morpholine and N-ethylmorpholine;
S5: the second distillate is sent to a thin film evaporator through a second discharge pipe 430 for rectification, the thin film evaporator comprises an evaporator 510 and a third condenser 520, in the evaporator 510, the evaporation temperature is 131 ℃, the vacuum degree is 89kpa, the evaporant is condensed through the third condenser 520 to obtain morpholine, N-ethyl morpholine is contained in the evaporator 510, and the purity of the morpholine is 99.8%.
the evaporator 510 has the same structure as that of embodiment 1.
Example 5:
a method for improving the purity of morpholine comprises the following steps: .
s1: at normal temperature, an aqueous morpholine solution is placed in a reactor 100 under the following reaction conditions: CO 22dropwise adding hydrogen peroxide under the atmosphere and the pH of 9, and reacting for 6 hours to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture;
The first mixture consists of morpholine, N-methylmorpholine oxide, N-ethylmorpholine, water and impurities;
S2: after the reaction of step S1, the obtained first mixture of products is heated slightly in the reactor 100 to precipitate crystals, and then filtered to obtain a second mixture;
the second mixture consists of morpholine, N-ethyl morpholine, water and impurities;
S3: adding solid sodium hydroxide into the obtained second mixture in a reactor 100, filtering, and then sending the second mixture into a first rectifying tower 200 through a connecting pipe 110, wherein the operating pressure of the first rectifying tower 200 is 100kpa, and the tower top temperature is 138 ℃; the temperature of the tower bottom is 155 ℃, the tower top is conveyed to a first condenser 220 through a first exhaust pipe 210 for condensation and collection to obtain a first distillate, and the first distillate is discharged through a first exhaust pipe 230;
the first distillate consists of morpholine, N-ethyl morpholine, a small amount of water and impurities;
s4: introducing the first distillate obtained in the step S3 into an extraction tower 300, adding n-octanol into the extraction tower 300 to obtain an extract phase, and sending the extract phase into a second rectifying tower 400 through an extraction discharge pipe 310 for rectification, wherein the operating pressure of the second rectifying tower 400 is 105kpa, and the tower top temperature is 140 ℃; the temperature of the tower bottom is 160 ℃, the tower top of the second rectifying tower 400 is connected with a second condenser 420 through a second exhaust pipe 410, and the second distillate is obtained by condensation and collection, wherein the process parameters of the extraction tower 300 are as follows: the operating pressure is 105kpa, and the extraction temperature is 90 ℃;
The main components of the second distillate are morpholine and N-ethylmorpholine;
s5: the second distillate is sent to a thin film evaporator through a second discharge pipe 430 for rectification, the thin film evaporator comprises an evaporator 510 and a third condenser 520, in the evaporator 510, the evaporation temperature is 132 ℃, the vacuum degree is 90kpa, the evaporant is condensed through the third condenser 520 to obtain morpholine, N-ethyl morpholine is contained in the evaporator 510, and the purity of the morpholine is 99.5%.
The evaporator 510 has the same structure as that of embodiment 1.
comparative example 1: a method for improving the purity of morpholine comprises the following steps: .
s1: at normal temperature, an aqueous morpholine solution is placed in a reactor 100 under the following reaction conditions: CO 22dropwise adding hydrogen peroxide under the atmosphere and the pH of 9, and reacting for 5 hours to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture;
The first mixture consists of morpholine, N-methylmorpholine oxide, N-ethylmorpholine, water and impurities;
s2: after the reaction of step S1, the obtained first mixture of products is heated slightly in the reactor 100 to precipitate crystals, and then filtered to obtain a second mixture;
The second mixture consists of morpholine, N-ethyl morpholine, water and impurities;
S3: adding solid sodium hydroxide into the obtained second mixture in a reactor 100, filtering, and then sending the second mixture into a first rectifying tower 200 through a connecting pipe 110, wherein the operating pressure of the first rectifying tower 200 is 100kpa, and the tower top temperature is 140 ℃; the temperature of the tower bottom is 155 ℃, the tower top is conveyed to a first condenser 220 through a first exhaust pipe 210 for condensation and collection to obtain a first distillate, and the first distillate is discharged through a first exhaust pipe 230;
the first distillate consists of morpholine, N-ethyl morpholine, a small amount of water and impurities;
s4: introducing the first distillate obtained in the step S3 into an extraction tower 300, adding paraxylene into the extraction tower 300 to obtain an extract phase, and sending the extract phase into a second rectifying tower 400 through an extraction discharge pipe 310 for rectification, wherein the operating pressure of the second rectifying tower 400 is 90kpa, and the tower top temperature is 130 ℃; the temperature of the tower bottom is 145 ℃, the tower top of the second rectifying tower 400 is connected with a second condenser 420 through a second exhaust pipe 410, and the second distillate is obtained by condensation and collection, wherein the process parameters of the extraction tower 300 are as follows: the operating pressure is 105kpa, and the extraction temperature is 90 ℃;
The main components of the second distillate are morpholine and N-ethylmorpholine;
S5: the second distillate is sent to a thin film evaporator through a second discharge pipe 430 for rectification, the thin film evaporator comprises an evaporator 510 and a third condenser 520, in the evaporator 510, the evaporation temperature is 135 ℃, the vacuum degree is 70kpa, the evaporant is condensed through the third condenser 520 to obtain morpholine, N-ethyl morpholine is contained in the evaporator 510, and the purity of the morpholine is 98.8%.
comparative example 2:
the existing purification method comprises the following steps: and (3) purifying the morpholine aqueous solution by four-tower rectification to obtain morpholine, wherein the purity of the morpholine is 98.7%.
description of the experiment:
The morpholine obtained in the experimental examples 1-5 and the comparative examples 1 and 2 is subjected to purity detection, the purity of the experimental examples 1-5 is more than 99%, the method provided by the invention is also adopted in the comparative example 1, but the evaporator device provided by the invention is not adopted, the purity of the comparative example 1 is obviously lower than that of the examples in terms of purity comparison, and the morpholine prepared in the comparative example 2 by the four-tower rectification method not only needs more energy consumption, but also is relatively lower than that of the morpholine prepared by the method provided by the invention in purity.
In conclusion, compared with the prior art, the purification method provided by the invention has the advantages of lower energy consumption and higher purity of the prepared product.
while embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (9)
1. A method for improving the purity of morpholine is characterized in that: the method comprises the following steps:
s1: at normal temperature, the morpholine aqueous solution is in pure CO2Dropwise adding hydrogen peroxide under the atmosphere and the pH of 7-9, and reacting for 5-6 hours to oxidize N-methylmorpholine into N-methylmorpholine oxide to obtain a first mixture; the first mixture consists of morpholine, N-methylmorpholine oxide, N-ethylmorpholine, water and impurities;
s2: after the reaction of step S1, the obtained first mixture of products is heated slightly to precipitate crystals, and filtered to obtain a second mixture; the second mixture consists of morpholine, N-ethyl morpholine, water and impurities;
s3: adding solid sodium hydroxide into the obtained second mixture, filtering, and then sending into a first rectifying tower, wherein the operating pressure of the first rectifying tower is 90-100 kpa, and the tower top temperature is 135-138 ℃; the temperature of the tower bottom is 150-155 ℃, and a first distillate is obtained by condensing and collecting the tower top; the first distillate consists of morpholine, N-ethyl morpholine, a small amount of water and impurities;
S4: introducing the first distillate obtained in the step S3 into an extraction tower, adding an extracting agent into the extraction tower to obtain an extraction phase, adding the extraction phase into a second rectifying tower for recovering the extracting agent, wherein the operating pressure of the second rectifying tower is 100-105 kpa, and the tower top temperature is 130-140 ℃; the temperature of the tower bottom is 155-160 ℃, the tower top is condensed and collected to obtain a second distillate, and the main components of the second distillate are morpholine and N-ethylmorpholine;
S5: and adding the second distillate into a thin film evaporator for rectification, wherein the evaporation temperature is 128-132 ℃, the evaporant is condensed by a condenser to obtain morpholine, and the substance obtained in the evaporator is N-ethylmorpholine.
2. the method for improving morpholine purity according to claim 1, characterized in that: the extractant is selected from n-heptanol, sec-octanol or n-octanol.
3. the method for improving morpholine purity according to claim 1, characterized in that: the process parameters of the extraction tower are as follows: the operating pressure is 100-105 kpa expressed by absolute pressure, and the extraction temperature is 80-90 ℃.
4. The method for improving morpholine purity according to claim 1, characterized in that: and recrystallizing the crystal precipitated in the step S2 by using acetone to obtain the N-methylmorpholine oxide hydrate.
5. the method for improving morpholine purity according to claim 1, characterized in that: the technological parameters of the evaporation film device during operation are as follows: the number of the scrapers is 4; the vacuum degree is 70-90 kpa.
6. morpholine prepared by the method for improving morpholine purity according to any one of claims 1-5.
7. the apparatus for improving morpholine purity according to claim 1, characterized in that: the device comprises a reactor, a first rectifying tower, an extraction tower, a second rectifying tower and a thin film evaporator which are connected in sequence;
The reactor is provided with a connecting pipe connected with a first rectifying tower, the top of the first rectifying tower is provided with a first exhaust pipe, and the free end of the first exhaust pipe is connected with a first condenser; a first discharge pipe of the first condenser is connected with the extraction tower, an extraction discharge pipe is arranged at the top of the extraction tower and connected with the second rectification tower, a second exhaust pipe is arranged at the top of the second rectification tower, and the free end of the second exhaust pipe is connected with a second condenser; the second condenser is provided with a second discharge pipe, and the second discharge pipe is connected with the thin film evaporator.
8. The apparatus for improving morpholine purity according to claim 6, characterized in that: the film evaporator comprises an evaporator and a third condenser, the evaporator comprises a shell, a heating shell used for introducing steam is arranged on the outer wall of the shell, a rotating shaft is arranged in the shell, a scraper component is arranged on the rotating shaft and comprises a rotor connected with the rotating shaft, the rotor is an eccentric wheel, and a first scraper blade and a second scraper blade are arranged on two sides of the rotor.
9. the apparatus for improving morpholine purity according to claim 8, characterized in that: the scraper components on the rotating shaft are two, and the two scraper components are arranged up and down.
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