CN110283144A - A kind of preparation method of morpholino b acid - Google Patents
A kind of preparation method of morpholino b acid Download PDFInfo
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- CN110283144A CN110283144A CN201910504839.1A CN201910504839A CN110283144A CN 110283144 A CN110283144 A CN 110283144A CN 201910504839 A CN201910504839 A CN 201910504839A CN 110283144 A CN110283144 A CN 110283144A
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- morpholino
- added dropwise
- ethionic
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- 239000002253 acid Substances 0.000 title claims abstract description 54
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- KHEVPDFAQFJIGK-UHFFFAOYSA-N 2-sulfooxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOS(O)(=O)=O KHEVPDFAQFJIGK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 29
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 9
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 230000008719 thickening Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 12
- 238000010612 desalination reaction Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- -1 quinoline ethanesulfonic acid sodium Chemical compound 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 208000012839 conversion disease Diseases 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical class CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- GSBCOIAKOZSVSE-UHFFFAOYSA-N ethanesulfonic acid;morpholine;sodium Chemical compound [Na].CCS(O)(=O)=O.C1COCCN1 GSBCOIAKOZSVSE-UHFFFAOYSA-N 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C07D295/04—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of morpholino b acid, are related to ethanesulfonic acid derivative product scope, comprising the following steps: step 1: sulfonation, and dehydrated alcohol is passed through sulfur trioxide gas under stirring cooling, generates ethionic acid；Ethionic acid is added drop-wise to deionized water to be diluted；Step 2: neutralizing, and liquid alkaline is added dropwise under stirring cooling in ethionic acid solution and generates ethionic acid sodium solution；Step 3: addition, ethionic acid sodium solution add morpholine under stiring, and liquid alkaline is added dropwise in heating, control reaction solution PH, and keep the temperature a period of time, generate morpholino b acid sodium；Step 4: acidification.Step 5: morpholino b acid aqueous solution enters the further separating sodium sulfate salt of electrodialytic membranes device, negative pressure thickening, and decrease temperature crystalline is centrifugated to obtain one water morpholino b acid product of solid, and centrifugate is recyclable to be inserted in concentration extraction product.The present invention improves synthesis condition, reduces the generation of reaction polymer, and reaction conversion ratio is improved by the 70% of original process to 95% with alcohol meter.
Description
Technical field
The present invention relates to ethanesulfonic acid derivative product scope more particularly to a kind of preparation methods of morpholino b acid.
Background technique
The synthesis of morpholino b acid using ethyl alcohol stirring cooling under be passed through at 0-50 DEG C sulfur trioxide gas (molar ratio 1:
2) ethionic acid, is generated, 30% liquid alkaline (molar ratio 1:3) is added and ethers polymerization inhibitor (molar ratio 1:0.005) is warming up to 50-60
DEG C ethionic acid reaction is added dropwise generates sodium vinyl sulfonate and sodium sulphate and polyvinylsulfonic acid sodium mixed liquor, refrigerated centrifuge separation
Sodium sulfate salt obtains vinyl sulfonic acid sodium solution, morpholine and vinyl sulfonic acid sodium solution (molar ratio 1:1) addition reaction, generates morpholine
Ethanesulfonic acid sodium, morpholino b acid sodium adsorb sodium ion by cationic resin column, and abjection is concentrated after collecting morpholino b acid solution
Moisture is centrifuged to obtain a water morpholino b acid solid after decrease temperature crystalline, with alcohol meter reaction conversion ratio for 70%.This synthetic technology is deposited
In following disadvantage: first, the synthesis process of feed ethylene base sodium sulfonate generates a large amount of polymerization impurity, causes crystallization centrifuge mother liquor
COD is very high, and biochemical treatment is at high cost；Second, resin column absorption acidification carries out after needing reaction solution diluting 5-10 times, sets simultaneously
The parsing of rouge column generates a large amount of acid waste water and washes, high production cost, environmental pollution are big；Third collects morpholine second
Contain acidic materials in sulfonic acid solutions concentration abjection moisture, is easy to generate corrosion and damage to production equipment.
Summary of the invention
The invention proposes a kind of preparation methods of morpholino b acid.
To achieve the goals above, present invention employs following technical solutions:
A kind of preparation method of morpholino b acid, comprising the following steps:
Step 1: sulfonation
Dehydrated alcohol is passed through sulfur trioxide gas under stirring cooling, generates ethionic acid；Ethionic acid is added drop-wise to
It is diluted in deionized water；
Step 2: it neutralizes
The stirring cooling of ethionic acid solution is lower to be added dropwise liquid alkaline generation ethionic acid sodium solution；
Step 3: addition
Ethionic acid sodium solution adds morpholine under stiring, and liquid alkaline is added dropwise in heating, controls reacting liquid temperature, PH, and alternating temperature
Heat preservation a period of time, generate morpholino b acid sodium water solution；
Step 4: acidification desalination
In morpholino b acid sodium water solution be added dropwise dilute sulfuric acid be acidified, be added deionized water dilution, decrease temperature crystalline from
Heart sal glauberi salt, obtains morpholino b acid；
Step 5: purifying crystal
Morpholino b acid aqueous solution enters the further separating sodium sulfate salt of electrodialytic membranes device, negative pressure thickening, cooling
Crystallization is centrifugated to obtain one water morpholino b acid product of solid, and centrifugate is recyclable to be inserted in concentration extraction product.
Further, the molar ratio of dehydrated alcohol and sulfur trioxide gas is 1:2 in the step 1.
Further, dehydrated alcohol is cooled to 0-50 DEG C in stirring in the step 1 and is passed through sulfur trioxide gas.
Further, the weight of the deionized water added in the step 1 is 1 times of ethionic acid weight.
Further, dilution ethionic acid is added dropwise in deionized water at 10-20 DEG C in the step 1.
Further, the liquid alkaline being added dropwise in the step 2 is 30% liquid alkaline of concentration.
Further, the stirring in ethionic acid solution is in 10-20 DEG C of dropwise addition liquid alkaline.
Further, the molar ratio of ethionic acid and liquid alkaline is 1:2 in the step 2.
Further, the molar ratio of ethylene sulfonate and liquid alkaline is 1:1 in the step 3.
Further, the molar ratio of ethylene sulfonate and morpholine is 1:1 in the step 3.
Further, it is warming up to 60 DEG C in the step 3, liquid alkaline is added dropwise again, control 60 DEG C of reacting liquid temperature, PH=8-
12.5, it is added dropwise to complete 60 DEG C and keeps the temperature 8 hours, be warming up to 100 DEG C of reflux and keep the temperature 4 hours, generate morpholino b acid sodium.
Further, it 49% dilute sulfuric acid is added dropwise in the step 4 in morpholino b acid sodium is acidified and be adjusted to Ph
4-4.5。
Further, deionized water is added in the step 4 and is diluted to 15% or less material content.
Further, 10-20 DEG C of crystallization sal glauberi salt centrifugation is cooled in the step 4.
Further, the morpholino b acid of generation is purified after the completion of the step 4, comprising the following steps: centrifugation
Liquid carries out residual sodium sulfate salt using electrodialytic membranes and is completely separated, and material negative pressure concentration abjection moisture to the material after desalination starts
It is precipitated, is cooled to 0 DEG C or less and is centrifuged to obtain a water morpholino b acid solid, centrifugate is recyclable to be inserted in concentration extraction product；
The present invention has following usefulness:
First, synthesis condition is improved, reduces the generation of reaction polymer, the conversion ratio of reaction is with alcohol meter by original process
70% improves to 95%；
Second, acidification desalination mode is improved, waste water is reduced and generates, former ton product generates waste water 30-36 tons of production, waste water
COD reaches 5-10 ten thousand, and improved 5-6 tons of production technology ton production waste water, waste water COD, can be directly as less than 20,000
Raw water carries out biochemical treatment qualified discharge.
Third, improved process route morpholino b acid solution abjection moisture are not containing acidic materials, will not be to life
It produces equipment and generates corrosion and damage, service life of equipment obviously increases.
Detailed description of the invention
Fig. 1 is the FTIR spectrogram of morpholino b acid original process；
Fig. 2 is the FTIR spectrogram of morpholino b acid new process.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.
A kind of reaction equation of the preparation method of morpholino b acid are as follows:
(1) sulfonation
Main reaction:
Side reaction:
(2) it neutralizes
Main reaction:
HSO3-CH2-CH2-O-SO3H+2NaOH→NaSO3-CH2-CH2-O-SO3Na+2H2O
Side reaction:
NaSO3-CH2-CH2-O-SO3Na+NaOH→NaSO3- CH=CH2+NaSO4+H2O
H2SO4+2NaOH→Na2SO4+2H2O
(3) addition
Main reaction:
Side reaction:
(4) it is acidified
Main reaction:
Side reaction:
Infrared qualitative analysis Fig. 1 and Fig. 2 matching degree are 99.86%.
Embodiment 1:
(1) dehydrated alcohol 64.4g is added, sulfur trioxide gas 224g is passed through at 0-50 DEG C under stirring cooling, generates second two
Sulfonic acid；
(2) it adds and is diluted under cooling down in 284.4g deionized water in 35-40 DEG C of dropwise addition ethionic acid；
(3) ethionic acid sodium solution is generated in 35-40 DEG C of 30% liquid alkaline 373.3g of dropwise addition under stirring cooling, is added under stirring
Morpholine 121.8g is warming up to 60 DEG C of 30% liquid alkaline 186.7g of dropwise addition, controls reaction solution PH=12.5-13.5, is added dropwise to complete 60 DEG C
Heat preservation 4 hours is warming up to 100 DEG C of reflux and keeps the temperature 4 hours, is cooled to 40 DEG C or less；
(4) 49% dilute sulfuric acid 142g is added dropwise and is acidified to PH=4.3, deionized water 400g is added and is diluted to material content 15%
Hereinafter, being cooled to 10-20 DEG C of crystallization sal glauberi salt centrifugation 386.4g；
(5) centrifugate using homogeneous membrane carry out residual sodium sulfate salt be completely separated to content less than 0.25%, after desalination
Material negative pressure concentration abjection moisture starts to be precipitated to material, is cooled to 0 DEG C or less and is centrifuged to obtain a water morpholino b acid solid 134g；
Centrifugate morpholino b acid 180g content 45.47% (with alcohol meter reaction conversion ratio for 74.48%), centrifugate is recyclable to be inserted in
Next group concentration and recovery product；
Testing product: content 99.38%PH value: 3.50 PKa:6.13 Pb:1.2ppm Fe:0.6ppm light absorption values:
250nm (10%): 0.006 appearance: white powder crystal
Embodiment 2:
(1) dehydrated alcohol 64.4g is added, sulfur trioxide gas 224g is passed through at 0-50 DEG C under stirring cooling, generates second two
Sulfonic acid；
(2) it adds and is diluted under cooling down in 284.4g deionized water in 10-20 DEG C of dropwise addition ethionic acid；
(3) ethionic acid sodium solution is generated in 10-20 DEG C of 30% liquid alkaline 373.3g of dropwise addition under stirring cooling, is added under stirring
Morpholine 121.8g is warming up to 60 DEG C of 30% liquid alkaline 186.7g of dropwise addition, controls reaction solution PH=12.5-13.5, is added dropwise to complete 60 DEG C
Heat preservation 8 hours is warming up to 100 DEG C of reflux and keeps the temperature 4 hours, is cooled to 40 DEG C or less；
(4) 49% dilute sulfuric acid 142g is added dropwise and is acidified to PH=4.3, deionized water 400g is added and is diluted to material content 15%
Hereinafter, being cooled to 10-20 DEG C of crystallization sal glauberi salt centrifugation 382g；
(5) centrifugate using homogeneous membrane carry out residual sodium sulfate salt be completely separated to content less than 0.25%, after desalination
Material negative pressure concentration abjection moisture starts to be precipitated to material, is cooled to 0 DEG C or less and is centrifuged to obtain a water morpholino b acid solid 150g；
Centrifugate morpholino b acid 200g content 45% (with alcohol meter reaction conversion ratio for 82.96%), centrifugate circulation can be inserted in down
A collection of concentration and recovery product；
Testing product: content 99.48%PH value: 3.55 PKa:6.18 Pb:1.3ppm Fe:0.8ppm light absorption values:
250nm (10%): 0.01 appearance: white powder crystal
Embodiment 3:
(1) dehydrated alcohol 64.4g is added, sulfur trioxide gas 224g is passed through at 0-50 DEG C under stirring cooling, generates second two
Sulfonic acid；
(2) it adds and is diluted under cooling down in 284.4g deionized water in 10-20 DEG C of dropwise addition ethionic acid；
(3) ethionic acid sodium solution is generated in 10-20 DEG C of 30% liquid alkaline 373.3g of dropwise addition under stirring cooling, is added under stirring
Morpholine 121.8g is warming up to 60 DEG C of 30% liquid alkaline 186.7g of dropwise addition, controls reaction solution PH=8-12.5, is added dropwise to complete 60 DEG C of heat preservations
It 8 hours, is warming up to 100 DEG C of reflux and keeps the temperature 4 hours, be cooled to 40 DEG C or less；
(4) 49% dilute sulfuric acid 142.4g is added dropwise and is acidified to PH=4.2, deionized water 400g is added and is diluted to material content
15% hereinafter, be cooled to 10-20 DEG C of crystallization sal glauberi salt centrifugation 380g；
(5) centrifugate using homogeneous membrane carry out residual sodium sulfate salt be completely separated to content less than 0.25%, after desalination
Material negative pressure concentration abjection moisture starts to be precipitated to material, is cooled to 0 DEG C or less and is centrifuged to obtain a water morpholino b acid solid 170g；
Centrifugate morpholino b acid 230g content 45.12% (with alcohol meter reaction conversion ratio for 95.17%), centrifugate circulation are inserted in down
A collection of concentration and recovery product；
Testing product: content 99.68%PH value: 3.38 PKa:6.15 Pb:1.3ppm Fe:0.7ppm light absorption values:
250nm (10%): 0.006 appearance: white powder crystal
Embodiment 4:
A kind of preparation method of morpholino b acid, comprising the following steps:
(1) dehydrated alcohol 64.4g is added, sulfur trioxide gas 224g is passed through at 0--50 DEG C under stirring cooling, generates second two
Sulfonic acid is added and is diluted under cooling down in 284.4g deionized water in 10-20 DEG C of dropwise addition ethionic acid；
(2) ethionic acid sodium solution is generated in 10-20 DEG C of 30% liquid alkaline 373.3g of dropwise addition under stirring cooling, is added under stirring
Morpholine 128.1g is warming up to 60 DEG C of 30% liquid alkaline 186.7g of dropwise addition, controls reaction solution PH=8-12.5, is added dropwise to complete 60 DEG C of heat preservations
It 4 hours, is warming up to 100 DEG C of reflux and keeps the temperature 4 hours, be cooled to 40 DEG C or less；
(3) 49% dilute sulfuric acid 142.4g is added dropwise and is acidified to PH=4.2, deionized water 400g is added and is diluted to material content
15% hereinafter, be cooled to 10-20 DEG C of crystallization sal glauberi salt centrifugation 382.5g；
(4) centrifugate carries out residual sodium sulfate salt using homogeneous membrane and is completely separated object to content less than 0.1%, after desalination
Material negative pressure concentration abjection moisture starts to be precipitated to material, is cooled to 0 DEG C or less centrifugation, centrifugation material is put in 60 DEG C of drying 16 in baking oven
Hour a water morpholino b acid solid 169g, centrifugate 217.3g, centrifugate test and analyze morpholino b acid content
45.12%, centrifugate circulation is inserted in next group concentration and recovery product；
With alcohol meter reaction conversion ratio for 92.56%.
Testing product: content 99.24%PH value: 3.35 PKa:6.15 Pb:1.1ppm Fe:0.5ppm light absorption values:
250nm (10%): 0.007 appearance: white powder crystal.
By identical material proportion, changing reaction condition test result be see the table below
During improving acidification desalination mode, former ton product generates the delta data of production waste water and waste water COD.
Former ton product generates waste water 30-36 tons of production, waste water COD=77250, improved production technology ton production
5-6 tons of waste water, waste water COD=9978.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of morpholino b acid, comprising the following steps:
Step 1: sulfonation
Dehydrated alcohol is passed through sulfur trioxide gas under stirring cooling, generates ethionic acid；Second two is added dropwise in deionized water
Sulfonic acid is diluted；
Step 2: it neutralizes
Liquid alkaline is added dropwise under stirring cooling in ethionic acid solution and generates ethionic acid sodium solution；
Step 3: addition
Ethionic acid sodium solution adds morpholine under stiring, and liquid alkaline is added dropwise in heating, controls reaction solution PH, and keep the temperature a period of time,
Generate morpholino b acid sodium；
Step 4: acidification desalination
Dilute sulfuric acid is added dropwise in morpholino b acid sodium to be acidified, deionized water dilution, decrease temperature crystalline sal glauberi salt is added
Centrifugation generates morpholino b acid aqueous solution；
Step 5: purifying crystal
Morpholino b acid aqueous solution enters the further separating sodium sulfate salt of electrodialytic membranes device, negative pressure thickening, decrease temperature crystalline
It is centrifugated to obtain one water morpholino b acid product of solid, centrifugate is recyclable to be inserted in concentration extraction product.
2. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that by nothing in the step 1
Water-ethanol is cooled to 0-50 DEG C in stirring and is passed through sulfur trioxide gas.
3. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that added in the step 1
The weight of deionized water be one times of ethionic acid weight.
4. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that gone in the step 1 from
Dilution ethionic acid is added dropwise in sub- water at 10-20 DEG C.
5. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that be added dropwise in the step 2
Liquid alkaline be 30% liquid alkaline.
6. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that described molten in ethionic acid
Stirring is in 10-20 DEG C of dropwise addition liquid alkaline in liquid.
7. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that heat up in the step 3
Liquid alkaline is added dropwise again to 60 DEG C, controls 60 DEG C of reacting liquid temperature, PH=8-12.5, is added dropwise to complete 60 DEG C and keeps the temperature 8 hours, be warming up to
100 DEG C of reflux keep the temperature 4 hours, generate morpholino b acid sodium.
8. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that in the step 4
It 49% dilute sulfuric acid is added dropwise in quinoline ethanesulfonic acid sodium is acidified and Ph is adjusted to 4-4.5.
9. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that be added in the step 4
Deionized water is diluted to 15% or less material content.
10. a kind of preparation method of morpholino b acid according to claim 1, which is characterized in that the step 5 is to life
At morpholino b acid purified, comprising the following steps: centrifugate using electrodialytic membranes carry out residual sodium sulfate salt thoroughly divide
From the material negative pressure concentration abjection moisture after desalination starts to be precipitated to material, is cooled to 0 DEG C or less and is centrifuged to obtain a water morpholine second sulphur
Sour solid, centrifugate circulation are inserted in concentration extraction product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104803949A (en) * | 2015-05-19 | 2015-07-29 | 山东理工大学 | Method for preparing high-purity 4-hydroxyethyl piperazine ethane sulfonic acid |
| CN109836399A (en) * | 2017-11-27 | 2019-06-04 | 荆楚理工学院 | A kind of synthetic method of biological buffer-morpholinoethanesulfonic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803949A (en) * | 2015-05-19 | 2015-07-29 | 山东理工大学 | Method for preparing high-purity 4-hydroxyethyl piperazine ethane sulfonic acid |
| CN109836399A (en) * | 2017-11-27 | 2019-06-04 | 荆楚理工学院 | A kind of synthetic method of biological buffer-morpholinoethanesulfonic acid |
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| DAVID S. BRESLOW ET. AL.: "Synthesis of Sodium Ethylenesulfonate from Ethanol", 《J. AM. CHEM. SOC.》 * |
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