CN109694337B - Sodium isethionate ellipsoidal crystal and preparation method thereof - Google Patents
Sodium isethionate ellipsoidal crystal and preparation method thereof Download PDFInfo
- Publication number
- CN109694337B CN109694337B CN201811377235.7A CN201811377235A CN109694337B CN 109694337 B CN109694337 B CN 109694337B CN 201811377235 A CN201811377235 A CN 201811377235A CN 109694337 B CN109694337 B CN 109694337B
- Authority
- CN
- China
- Prior art keywords
- sodium isethionate
- temperature
- crystal
- ellipsoidal
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Abstract
The invention discloses an ellipsoidal crystal of sodium isethionate and a preparation method thereof. Adding the coarse product of the sodium isethionate into water to prepare suspension with a certain concentration, adding a certain proportion of gallic acid as an additive, heating to 80-100 ℃, and stirring to dissolve the system clearly. The sodium isethionate solution was concentrated to some extent by evaporation under programmed reduced pressure. Then growing the crystal for a period of time, and cooling the system to 10-25 ℃ in a program temperature control mode. And obtaining ellipsoidal sodium isethionate crystals through centrifugation, washing and drying. The main grain diameter of the ellipsoidal crystal is 500-700 μm, and the bulk density is 1.10-1.30 g/mL. The method has high production efficiency and simple process flow, and is easy to realize industrialization.
Description
Technical Field
The invention relates to the technical field of chemical medicine crystallization, in particular to an ellipsoidal crystal of sodium isethionate and a preparation method thereof.
Background
Taurine, a naturally pure β -sulfonated amino acid, is a sulfur-containing amino acid essential for human and mammalian body activities. Although not directly participating in the synthesis of proteins and enzymes in vivo, the lipid-lowering peptide has important physiological functions of treating fatty liver, relieving heart failure, eliminating fatigue and the like, so that the lipid-lowering peptide is widely applied to the food and medicine industries.
The taurine synthesis method mainly comprises an ethanolamine method and an ethylene oxide method. Among them, the ethanolamine method is gradually eliminated due to long reaction period, low conversion rate and high cost. The ethylene oxide method has high conversion rate and convenient continuous production, and becomes a main process route for producing taurine in China at present. In the process of producing taurine by an ethylene oxide method, sodium isethionate is the most important synthetic intermediate.
The sodium isethionate is an organic sodium salt of isethionic acid, is mainly used as a surfactant intermediate, an intermediate of daily chemicals, medicines, fine chemicals and the like, and is widely applied in the field of chemical organic synthesis. Sodium isethionate is a white acicular or long rod crystal that is readily soluble in water at room temperature. The prior sodium isethionate crystal product sold in the market has the problems of small particle size, uneven distribution, low bulk density, poor preparation performance, large length-diameter ratio, easy breakage and the like, and causes great trouble for downstream product application.
Patent CN201010566737.1 describes a process for preparing sodium isethionate by reacting sodium bisulfite solution with ethylene oxide. The method mainly focuses on the aspects of improving the conversion rate, improving the purity of the sodium hydroxide, reducing the reaction energy consumption and the like, and does not mention the crystallographic indexes of the product such as bulk density, fluidity, caking, particle size distribution and the like.
At present, most of researchers and production technicians pay attention to the upstream synthesis aspect of the sodium isethionate, and the downstream purification and refining, such as the crystallography property problem, are rarely researched. This seriously affects the industrial application and market competitiveness of the product.
Therefore, there is a need to develop a method that can improve the crystallographic properties of sodium isethionate.
Disclosure of Invention
The invention aims to develop a method for preparing a sodium isethionate crystal product with good crystallographic properties aiming at the problems of small particle size, uneven distribution, low bulk density, poor preparation performance, large length-diameter ratio, easy breakage and the like of the sodium isethionate crystal product in the prior art. The method has high production efficiency and simple process flow, and is easy to realize industrialization.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of an ellipsoidal crystal of sodium isethionate comprises the following steps: adding the coarse product of the sodium isethionate into water to prepare suspension with a certain concentration, adding a certain proportion of gallic acid as an additive, heating to 80-100 ℃, preferably 85-95 ℃, and stirring to dissolve the system clearly; evaporating and concentrating the sodium isethionate solution to a certain degree in a programmed pressure reduction manner; growing crystals for a period of time, and cooling the system to 10-25 ℃, preferably 15-20 ℃ in a program temperature control manner; and obtaining ellipsoidal sodium isethionate crystals through centrifugation, washing and drying.
In the preparation method, the evaporation-cooling coupling crystallization process is adopted for crystallization.
The concentration of the suspension is 35-55 wt%, preferably 40-50 wt%.
The content of the additive is 500ppm to 10000ppm, preferably 2000ppm to 5000 ppm.
Preferably, the pressure reduction process is performed by using a diaphragm vacuum pump, and the pressure reduction process of the diaphragm vacuum pump of the invention is as follows: the pressure is gradually and linearly reduced from 0.1MPa to 0.01MPa, and the pressure reduction time is 1-4 h.
The end point of the evaporation concentration is 50-65 wt%, preferably 56-63 wt%.
The stirring is stopped during the crystal growing, and the time is 1-3 h.
Preferably, the program temperature control is realized by a thermostatic bath, and the temperature control program of the thermostatic bath is as follows: the temperature is gradually and linearly reduced from the crystal growing temperature to 10-25 ℃, preferably 15-20 ℃, and the cooling rate is 6-30 ℃/h.
The rotating speed of the centrifuge is 1000-3000 rpm.
The drying method adopts spray drying, the inlet temperature is 150-200 ℃, and the outlet temperature is 80-90 ℃.
The invention further relates to the sodium isethionate ellipsoidal crystal prepared by the above method, the primary particle size is 500 to 700 μm, and the bulk density is 1.10 to 1.30 g/mL.
The invention has the positive effects that:
firstly, gallic acid is selected as an additive to influence the nucleation and growth processes of the sodium isethionate crystal, and finally the crystal is expressed in an ellipsoidal crystal form. The hydroxyethyl sodium sulfonate has extremely high solubility in water, but has extremely narrow metastable zone, and is easy to spontaneously and rapidly crystallize, so that the nucleation process of the crystals is difficult to control, and long rod-shaped or needle-shaped crystals are mostly formed. The gallic acid, as a polyhydroxy aromatic carboxylic acid, has a relatively obvious promotion effect on the solubility of the sodium isethionate in a water solvent system, so that the metastable zone of crystallization is objectively widened, and the controllability is enhanced. The slow change of supersaturation of the system, whether due to evaporation or cooling, can be controlled to allow the growth of the nucleated crystals to proceed toward the desired crystal habit, rather than continuing to nucleate in large quantities.
Secondly, combining two solution crystallization modes with different mechanisms, namely evaporation crystallization and cooling crystallization, to form an evaporation-cooling coupled crystallization process. Evaporative crystallization is the supersaturation produced by evaporation of the solvent and cooling the crystals by lowering the temperature. In contrast, the mode of evaporative crystallization enables the supersaturation degree of the system to be always maintained in a controllable range, and more round granular crystals are easier to generate. If evaporative crystallization is used solely to prepare sodium isethionate crystals, the energy consumption is extremely high. Considering that the solubility of the hydroxyethyl sodium sulfonate in water has a certain corresponding change trend along with the temperature change, the hydroxyethyl sodium sulfonate can be coupled in a simultaneous cooling crystallization mode, so that the energy consumption of the crystallization process is reduced as much as possible on the basis of ensuring the relatively round granular crystal habit of the crystal, and the process yield is improved.
Thirdly, successfully preparing a novel ellipsoid crystal habit of sodium isethionate which is relatively round and smooth. Comparing the ellipsoidal crystal with the long rod-like crystal prepared by the industrially available method, it can be easily found that: the former has larger main particle size, higher mass purity and higher bulk density. The novel ellipsoidal crystal with high bulk density and large particle size shows more excellent crystallography properties and wider application field in the subsequent industrial application of the sodium isethionate, such as preparation, processing and the like.
Drawings
FIG. 1 is a microscope photograph of the sodium isethionate ellipsoidal crystal habit product obtained in example 4;
FIG. 2 is an X-ray powder diffraction pattern of the sodium isethionate ellipsoidal crystal habit product obtained in example 4;
FIG. 3 is a microscopic image of the sodium isethionate product obtained in comparative example 1.
Detailed Description
The following examples are intended to illustrate the invention without limiting it in any way.
The analysis method comprises the following steps: a Wantong 883 full-automatic ion chromatograph; separation column IonPacAS11-HC (4 mm. times.250 mm); the column temperature is 30 ℃; a conductance detector; the mobile phase is 5.0mmol/L sodium carbonate solution, the flow rate is 1.0mL/min, and the mobile phase of the inhibitor is 80mmol/L phosphoric acid water solution; the sample size was 25 uL.
The raw material sources are used:
a crude product of sodium isethionate with a chemical purity of 99%, alatin reagent, ltd;
gallic acid, chemical purity of 99%, Aladdin reagent Co.
Example 1
Preparing a suspension of 40% sodium isethionate in water, adding 500ppm gallic acid, heating to 85 deg.C, and stirring to dissolve the system. The pressure of the system is controlled by a diaphragm vacuum pump, and the system is gradually and linearly reduced from 0.1MPa to 0.01MPa in 1h, and is concentrated to 56 percent. Stopping stirring, and growing the crystal for 1 h. And then the temperature is gradually and linearly reduced to 25 ℃ through a constant temperature bath at the temperature reduction rate of 6 ℃/h. And centrifuging, washing and spray drying the crystal slurry to obtain ellipsoidal sodium isethionate crystals. The product had a major particle size of 520 μm and a bulk density of 1.10 g/mL.
Example 2
Preparing a suspension of 50% sodium isethionate in water, adding 10000ppm of gallic acid, heating to 95 ℃, and stirring to dissolve the system. The pressure of the system is controlled by a diaphragm vacuum pump, and the system is gradually and linearly reduced from 0.1MPa to 0.01MPa in 4h, and is concentrated to 63 percent. Stopping stirring, and growing the crystal for 3 h. And then the temperature is gradually and linearly reduced to 15 ℃ through a constant temperature bath at the temperature reduction rate of 30 ℃/h. And centrifuging, washing and spray drying the crystal slurry to obtain ellipsoidal sodium isethionate crystals. The product had a primary particle size of 708 μm and a bulk density of 1.31 g/mL.
Example 3
Preparing suspension of hydroxyethyl sodium sulfonate with concentration of 42% in water, adding 2000ppm of gallic acid, heating to 90 deg.C, and stirring to dissolve the system. The pressure of the system is controlled by a diaphragm vacuum pump, and the system is gradually and linearly reduced from 0.1MPa to 0.01MPa within 2h, and is concentrated to 58%. Stopping stirring, and growing the crystal for 2 h. Then the temperature is gradually and linearly reduced to 20 ℃ through a constant temperature bath at the temperature reduction rate of 10 ℃/h. And centrifuging, washing and spray drying the crystal slurry to obtain ellipsoidal sodium isethionate crystals. The product had a major particle size of 572 μm and a bulk density of 1.14 g/mL.
Example 4
Preparing a suspension of 45% sodium isethionate in water, adding 5000ppm gallic acid, heating to 92 ℃, and stirring to dissolve the system. The pressure of the system is controlled by a diaphragm vacuum pump, and the pressure is gradually and linearly reduced from 0.1MPa to 0.01MPa within 3h, so that the system is concentrated to 60%. Stopping stirring, and growing the crystal for 1.5 h. And then the temperature is gradually and linearly reduced to 20 ℃ through a constant temperature bath at the temperature reduction rate of 15 ℃/h. And centrifuging, washing and spray drying the crystal slurry to obtain ellipsoidal sodium isethionate crystals. The primary particle size of the product was 653 μm and the bulk density was 1.26 g/mL.
Example 5
Preparing a suspension of 48% sodium isethionate in water, adding 7000ppm gallic acid, heating to 95 deg.C, and stirring to dissolve the system. The pressure of the system is controlled by a diaphragm vacuum pump, and the system is gradually and linearly reduced from 0.1MPa to 0.01MPa in 3h, and is concentrated to 58%. Stopping stirring, and growing the crystal for 1.5 h. And then the temperature is gradually and linearly reduced to 15 ℃ through a constant temperature bath at the temperature reduction rate of 8 ℃/h. And centrifuging, washing and spray drying the crystal slurry to obtain ellipsoidal sodium isethionate crystals. The product had a primary particle size of 546 μm and a bulk density of 1.18 g/mL.
Example 6
Preparing a suspension of 46% sodium isethionate in water, adding 1000ppm gallic acid, heating to 95 deg.C, and stirring to dissolve the system. The pressure of the system was controlled by a diaphragm vacuum pump, and the system was concentrated to 56% by a stepwise linear decrease from 0.1MPa to 0.01MPa within 1.5 h. Stopping stirring, and growing the crystal for 2 h. Then the temperature is gradually and linearly reduced to 10 ℃ through a constant temperature bath at the temperature reduction rate of 12 ℃/h. And centrifuging, washing and spray drying the crystal slurry to obtain ellipsoidal sodium isethionate crystals. The product had a major particle size of 646 μm and a bulk density of 1.24 g/mL.
Comparative example 1
Preparing a suspension of 45% sodium isethionate in water, heating to 90 ℃, and stirring to dissolve the system clearly. The temperature of the system is directly reduced to 10 ℃ through a constant temperature bath. Filtering, washing and drying the crystal slurry to obtain the acicular and long rod-shaped sodium isethionate crystals. The product had a primary particle size of 332 μm and a bulk density of 0.76 g/mL.
Claims (10)
1. A method for preparing ellipsoidal crystals of sodium isethionate is characterized in that: adding the coarse product of the sodium isethionate into water to prepare suspension with the concentration of 35-55 wt%, adding gallic acid serving as an additive, heating to 80-100 ℃, and stirring to dissolve the system clearly; evaporating and concentrating the sodium isethionate solution to 50-65 wt% in a programmed pressure reduction mode; growing the crystal for 1-3 h, and cooling the system to 10-25 ℃ in a program temperature control mode; obtaining ellipsoidal sodium isethionate crystals through centrifugation, washing and drying; the crystallization adopts an evaporation-cooling coupling crystallization process; the content of the additive is 500 ppm-10000 ppm.
2. The method according to claim 1, characterized in that gallic acid is added as an additive, the temperature is raised to 85-95 ℃, and the system is stirred to be clear; then growing crystal, and cooling the system to 15-20 ℃ in a program temperature control mode.
3. The method of claim 1, wherein the suspension has a concentration of 40% to 50% by weight.
4. The method of claim 1, wherein the additive is present in an amount of 2000ppm to 5000 ppm.
5. A method according to any one of claims 1-3, characterized in that the programmed pressure reduction uses a diaphragm vacuum pump, the pressure reduction program of which is: the pressure is gradually and linearly reduced from 0.1MPa to 0.01MPa, and the pressure reduction time is 1-4 h.
6. The method according to claim 1, wherein the end point of the evaporative concentration is 56 to 63 wt%.
7. A method according to any one of claims 1 to 3, wherein stirring is stopped during seeding.
8. The method according to any one of claims 1 to 3, wherein the temperature control program is performed by a thermostat, and the temperature control program of the thermostat is: the temperature is gradually and linearly reduced from the crystal growing temperature to 10-25 ℃, and the cooling rate is 6-30 ℃/h.
9. The method of claim 8, wherein the temperature is gradually and linearly decreased from the seeding temperature to 15-20 ℃.
10. A method according to any one of claims 1 to 3, wherein the rotation speed of the centrifuge is 1000 to 3000 rpm; the drying mode adopts spray drying, the inlet temperature is 150-200 ℃, and the outlet temperature is 80-90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811377235.7A CN109694337B (en) | 2018-11-19 | 2018-11-19 | Sodium isethionate ellipsoidal crystal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811377235.7A CN109694337B (en) | 2018-11-19 | 2018-11-19 | Sodium isethionate ellipsoidal crystal and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109694337A CN109694337A (en) | 2019-04-30 |
| CN109694337B true CN109694337B (en) | 2022-04-22 |
Family
ID=66229839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811377235.7A Active CN109694337B (en) | 2018-11-19 | 2018-11-19 | Sodium isethionate ellipsoidal crystal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109694337B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112424176A (en) * | 2020-09-21 | 2021-02-26 | 安徽金禾实业股份有限公司 | Refining method of acesulfame potassium |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050764B (en) * | 2010-11-27 | 2012-05-23 | 吉林众鑫化工集团有限公司 | Method for purifying sodium hydroxyethyl sulphonate |
| US9428451B2 (en) * | 2014-04-18 | 2016-08-30 | Songzhou Hu | Cyclic process for the production of taurine from alkali isethionate |
-
2018
- 2018-11-19 CN CN201811377235.7A patent/CN109694337B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109694337A (en) | 2019-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2678585C2 (en) | Method of continuous preparation of methionine crystals of high bulk density | |
| CN109694337B (en) | Sodium isethionate ellipsoidal crystal and preparation method thereof | |
| CN104743581A (en) | Preparation technique of high-purity potassium chloride | |
| CN111905398A (en) | Process for producing nickel cobalt salt and ammonium salt by continuous crystallization | |
| CN112574263A (en) | Preparation method of psicose crystal | |
| CN104926709A (en) | L-tryptophan refining method | |
| CN105495528B (en) | A method of preparing high heap density the sapidity nucleotide disodium mixed crystal | |
| CN109694336B (en) | Rhombic taurine crystal and preparation method thereof | |
| CN111909179B (en) | Preparation method for improving morphological index of cefalexin crystal | |
| WO2022151995A1 (en) | New crystal form of γ-aminobutyric acid and preparation method therefor | |
| CN104355990B (en) | Method for recycling and mechanically using L- (+) -tartaric acid in D-ethyl ester production | |
| CN110114333B (en) | Improved synthesis of lysine acetylsalicylate glycine particles | |
| CN110527854A (en) | Method for preparing particle size controllable ultra-pure ammonium rhenate crystal | |
| CN110606863B (en) | Preparation method of N-acetylneuraminic acid dihydrate | |
| CN109574886A (en) | The taurine crystal and preparation method thereof that a kind of heap density, mobility are improved and do not coalesced | |
| CN109896971B (en) | Preparation method of gamma-aminobutyric acid | |
| CN101391967A (en) | Method for producing acrylic amide crystal | |
| CN112851492A (en) | Method for recovering benzoic acid from sodium benzoate-containing wastewater | |
| CN113993841B (en) | Process for the preparation of D, L-methionine | |
| CN112390236A (en) | Production method of acid potassium dihydrogen phosphate | |
| CN110305033A (en) | A kind of purification process of cilastatin sodium intermediate | |
| WO2023276980A1 (en) | Method for producing aspartic acid | |
| WO2023174422A1 (en) | High-purity crystalline d-tagatose, composition comprising same, method for preparing same, and use thereof | |
| CN117166062B (en) | Preparation method of magnesium sulfate whisker | |
| JP2024001848A (en) | Cyclic preparation method for columnar taurine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |