CN112521425B - Method for preparing glucosamine sulfate - Google Patents
Method for preparing glucosamine sulfate Download PDFInfo
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- CN112521425B CN112521425B CN202011472874.9A CN202011472874A CN112521425B CN 112521425 B CN112521425 B CN 112521425B CN 202011472874 A CN202011472874 A CN 202011472874A CN 112521425 B CN112521425 B CN 112521425B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C07H5/04—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to nitrogen
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Abstract
The invention relates to a method for preparing glucosamine sulfate, which comprises the following steps: i) reacting glucosamine hydrochloride with an organic alcohol; ii) mixing the obtained hydrochloride glucosamine solution with an adsorbent, then adding dilute sulfuric acid, and separating the adsorbent in the alcohol solution after adsorption is finished; iii) removing the alcohol solvent in the obtained alcoholic solution containing glucosamine sulfate to obtain the final product. The preparation of the adsorbent comprises the following steps: 1) respectively dissolving micron-sized silicon dioxide powder and nano-sized calcium carbonate powder in a solvent to prepare suspension, and then mixing the two suspensions to obtain mixed suspension; 2) immersing the cellulose acetate cotton core into the mixed suspension, and then drying the cotton core; 3) and sintering the dried cotton core, immersing the obtained adsorbent into acid liquor for etching after the sintering is finished, and then taking out the adsorbent to wash and remove the residual acid liquor to obtain the cotton core. The surface structure of the acetate fiber silk is reversely copied on the inner surface of the adsorbent, so that the chlorine content in glucosamine sulfate can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of glucosamine preparation, in particular to a method for preparing glucosamine sulfate.
Background
The following in the background art merely refers to information that is understood by the inventor to be relevant to the present invention and is intended to augment understanding of the present invention through a description of some basic technical knowledge related to the present invention, which information does not necessarily have to constitute knowledge that is well known by those of ordinary skill in the art.
Glucosamine is an essential component in proteoglycan synthesis in the matrix of human articular cartilage, because amino monosaccharides stimulate chondrocytes to produce glycoproteins with normal multimeric structures, inhibit certain enzymes that damage articular cartilage, inhibit the production of superoxide radicals in damaged cells, and prevent corticosteroids and certain non-steroidal anti-inflammatory drugs from damaging chondrocytes, reducing the release of endotoxin from damaged cells.
Glucosamine sulfate is commonly used to treat osteoarthritis in the knee, shoulder, spinal joint, hip, wrist, neck, ankle, and the like. However, glucosamine sulfate often contains impurities such as chloride ions left when glucosamine hydrochloride is prepared, and excessive chloride ions are likely to cause side effects after administration, and the purity of glucosamine sulfate is also influenced due to the high content of the impurities, which affects the therapeutic effect.
Disclosure of Invention
The invention mainly aims to provide a method capable of effectively reducing chloride ions in glucosamine sulfate, and in order to achieve the purpose, the invention discloses the following technical scheme:
in a first aspect of the present invention, there is provided a porous tubular adsorbent preparation method comprising the steps of:
(1) respectively dissolving micron-sized silicon dioxide powder and nano-sized calcium carbonate powder in a solvent to prepare suspension, and then mixing the two suspensions to obtain mixed suspension;
(2) immersing the cellulose acetate cotton core into the mixed suspension, and then drying the cellulose acetate cotton core;
(3) and sintering the dried cellulose acetate cotton core under a vacuum condition, immersing the obtained adsorbent into acid liquor for etching after the sintering is finished, and then taking out the adsorbent to wash and remove the residual acid liquor to obtain the cellulose acetate cotton core.
Preferably, in the step (1), the solvent includes at least one of distilled water, deionized water, ethanol, and the like. The micron-sized silicon dioxide is beneficial to obtaining the adsorbent with a relatively rough surface, and the nano-sized calcium carbonate powder can form micro-nano holes after subsequent treatment, so that more adsorption sites are provided.
Preferably, in the step (1), the ratio of the silica, the calcium carbonate and the solvent is 1g: 8-12 mL. The addition amount of the solvent is required to ensure that suspension is formed, the concentration of the silicon dioxide and the calcium carbonate cannot be too low, otherwise, the step (2) is required to be repeated for multiple times, and the phenomenon that the tubular structure of the adsorbent is easily collapsed and damaged in the subsequent sintering process due to too little silicon dioxide and calcium carbonate coated on the surface of the acetate fiber yarn is avoided.
Preferably, in the step (1), the suspension is stirred by ultrasound, so that the agglomeration of micron-sized silicon dioxide and calcium carbonate is avoided, firstly, the micron-sized silicon dioxide and calcium carbonate cannot be fully immersed in the cellulose acetate cotton core, and secondly, the microstructure of the surface of the adsorbent is influenced.
Preferably, in the step (1), the molar ratio of the silicon dioxide to the calcium carbonate in the mixed suspension is 3-7: 1. The porous tubular adsorbent prepared by the invention takes silicon dioxide as a main body to form good mechanical property, and is prevented from being easily damaged.
Preferably, in the step (2), the cellulose acetate cotton core is immersed into the mixed suspension and then ultrasonically vibrated, so that the silica and calcium carbonate particles are fully immersed into the cellulose acetate cotton core.
Preferably, in the step (2), the step of immersing → drying the dried acetate cotton core in the mixed suspension is repeated; optionally, the above steps are repeated at least three times.
Preferably, in the step (2), the drying temperature is 45-60 ℃, the time is not less than 30min, and the proper drying time and temperature can be selected according to the specification and size of the cellulose acetate cotton core.
Preferably, in the step (3), the sintering temperature is 550-900 ℃ and the sintering time is 0.5-1.5 h. The acetate fiber filaments wrapped in the silicon dioxide and the calcium carbonate are removed through a high-temperature sintering step, and simultaneously the calcium carbonate is decomposed, so that the adsorbent with a hollow tubular structure is formed.
Preferably, in the step (3), the acid solution comprises any one of dilute hydrochloric acid, dilute sulfuric acid, acetic acid and the like, preferably dilute sulfuric acid, so as to avoid introducing impurity ions. After acid etching, calcium oxide formed after calcium carbonate decomposition or residual calcium carbonate can be stripped from the adsorbent to form a porous structure.
In a second aspect of the present invention, there is disclosed a process for preparing glucosamine sulfate comprising the steps of:
(i) the hydrochloride glucosamine and the organic alcohol are mixed to obtain the hydrochloride glucosamine solution.
(ii) And mixing the hydrochloride glucosamine alcohol solution with the adsorbent, adding dilute sulfuric acid, and separating the adsorbent from the alcohol solution after adsorption to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And removing the alcohol solvent in the alcoholic solution containing the glucosamine sulfate to obtain the glucosamine sulfate.
Preferably, in step (i), the alcoholic solution of glucosamine hydrochloride includes a mixture of glucosamine hydrochloride and one of ethanol and propanol.
Preferably, in the step (ii), the mixing ratio of the adsorbent to the hydrochloride glucosamine solution is 3-5 g: 10-15 mL.
Preferably, in step (ii), the method of separation comprises at least one of centrifugation, filtration, and the like.
Preferably, in step (iii), the solvent is removed by a method including evaporation drying, distillation under reduced pressure, or the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the cross section of the acetate fiber yarn is similar to a multi-petal flower-shaped structure, the acetate fiber cotton core is used as a carrier, and after silicon dioxide and calcium carbonate attached to the surface of the acetate fiber yarn are sintered, an adsorbent block with a capillary-shaped structure is obtained, the surface structure of the acetate fiber yarn is reversely copied on the inner surface of the adsorbent, the inner surface of the adsorbent presents a concave-convex structure, and the structural characteristics endow the adsorbent with huge specific surface area and stronger adsorption capacity. Simultaneously, make the adsorbent be porous structure or the surface is pit-shaped structure after etching through the component that sets up in advance in to the adsorbent, these structural feature not only provide more adsorption sites for the adsorbent, the solution circulation of also being convenient for helps the chloride ion in the high-efficient quick adsorption solution more.
(2) The surface of the adsorbent is porous or pit-shaped by adopting the silicon dioxide and the calcium carbonate with the grain diameter having the grade difference, the micron-grade silicon dioxide can make the surface of the adsorbent rougher so as to create larger surface area, meanwhile, the nano-grade calcium carbonate can create nano-grade micron-grade micropores or pits after being etched by acid liquor through decomposition, and the structures can effectively increase adsorption sites on the surface of the adsorbent and improve the adsorption capacity of the adsorbent. In addition, the sintered silicon dioxide has better mechanical strength and long service life, and can be recycled after being desorbed by water washing, so that the loss of the adsorbent in the using process is reduced, and the adsorbent can be recycled conveniently.
(3) The invention adopts a method of adsorbing in an alcohol solution, inorganic salts such as sodium chloride and the like are not dissolved in organic alcohol such as ethanol and the like, so that chloride ions in the hydrochloride glucosamine are more concentrated, namely, the concentration of local chloride ions is increased, and the adsorption of the adsorbent to the chloride ions is promoted.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. The invention will now be further illustrated by specific examples.
Example 1
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing micron-sized silicon dioxide powder with deionized water according to the proportion of 1g to 10mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) Mixing nano calcium carbonate powder with deionized water according to the proportion of 1g to 10mL, and uniformly stirring to prepare calcium carbonate suspension for later use.
(3) And (3) mixing the two suspensions prepared in the steps (1) and (2) according to the molar ratio of the silicon dioxide to the calcium carbonate of 5:1, and then carrying out ultrasonic stirring to obtain a mixed suspension.
(4) And (3) immersing the cellulose acetate cotton core into the mixed suspension obtained in the step (3) and carrying out ultrasonic vibration for 15min, then taking out the cellulose acetate cotton core, drying for 45min at 50 ℃, and repeating the step for three times.
(5) And (3) placing the cellulose acetate cotton core dried in the step (4) in a vacuum tube furnace, sintering the cellulose acetate cotton core in vacuum at 650 ℃ for 1h, immersing the obtained adsorbent into dilute sulfuric acid for etching, taking out the adsorbent after no bubbles are generated in the dilute sulfuric acid, and washing the adsorbent for 3 times by using clear water to remove the acid liquor remaining in the adsorbent, thereby obtaining the capillary porous adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) Mixing the glucosamine hydrochloride solution obtained in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) of the embodiment according to the proportion of 12mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Example 2
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing micron-sized silicon dioxide powder with deionized water according to the proportion of 1g to 12mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) Mixing nano calcium carbonate powder with deionized water according to the proportion of 1g to 12mL, and uniformly stirring to prepare calcium carbonate suspension for later use.
(3) And (3) mixing the two suspensions prepared in the steps (1) and (2) according to the molar ratio of the silicon dioxide to the calcium carbonate of 7:1, and then carrying out ultrasonic stirring to obtain a mixed suspension.
(4) And (3) immersing the cellulose acetate cotton core into the mixed suspension obtained in the step (3) and carrying out ultrasonic vibration for 20min, then taking out the cellulose acetate cotton core, drying the cellulose acetate cotton core for 35min at the temperature of 55 ℃, and repeating the step for three times in total.
(5) And (3) placing the cellulose acetate cotton core dried in the step (4) in a vacuum tube furnace, sintering the cellulose acetate cotton core at 550 ℃ for 1.5h in vacuum, immersing the obtained adsorbent in dilute sulfuric acid for etching, taking out the adsorbent after no bubbles are generated in the dilute sulfuric acid, and washing the adsorbent for 3 times by using clear water to remove the residual acid liquid in the adsorbent, thereby obtaining the capillary porous adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) Mixing the hydrochloride glucosamine alcohol solution obtained in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) of the embodiment according to the proportion of 15mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2.5h, and filtering the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Example 3
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing micron-sized silicon dioxide powder with ethanol according to the proportion of 1g to 8mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) Mixing nano calcium carbonate powder with ethanol according to the proportion of 1g to 8mL, and uniformly stirring to prepare calcium carbonate suspension for later use.
(3) And (3) mixing the two suspensions prepared in the steps (1) and (2) according to the molar ratio of silicon dioxide to calcium carbonate of 4:1, and then carrying out ultrasonic stirring to obtain a mixed suspension.
(4) And (3) immersing the cellulose acetate cotton core into the mixed suspension obtained in the step (3) and carrying out ultrasonic vibration for 20min, then taking out the cellulose acetate cotton core, drying the cellulose acetate cotton core for 40min at the temperature of 45 ℃, and repeating the step for three times.
(5) And (3) placing the cellulose acetate cotton core dried in the step (4) in a vacuum tube furnace, sintering for 0.5h at 850 ℃ in vacuum, immersing the obtained adsorbent in acetic acid for etching, taking out the adsorbent after no bubbles are generated in the acetic acid, and washing the adsorbent for 3 times by using clear water to remove the acid liquor remaining in the adsorbent, thereby obtaining the capillary porous adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and propanol were mixed in a ratio of 1g to 10ml to obtain a hydrochloride glucosamine solution.
(ii) Mixing the glucosamine hydrochloride solution obtained in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) of the embodiment according to the proportion of 10mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering out the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Example 4
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing micron-sized silicon dioxide powder with ethanol according to the proportion of 1g to 11mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) Mixing nano calcium carbonate powder with ethanol according to the proportion of 1g to 11mL, and uniformly stirring to prepare calcium carbonate suspension for later use.
(3) And (3) mixing the two suspensions prepared in the steps (1) and (2) according to the molar ratio of the silicon dioxide to the calcium carbonate of 3:1, and then carrying out ultrasonic stirring to obtain a mixed suspension.
(4) And (3) immersing the cellulose acetate cotton core into the mixed suspension obtained in the step (3) and carrying out ultrasonic vibration for 15min, then taking out the cellulose acetate cotton core, drying the cellulose acetate cotton core for 30min at the temperature of 60 ℃, and repeating the step for three times.
(5) And (3) placing the cellulose acetate cotton core dried in the step (4) in a vacuum tube furnace, sintering for 0.5h at 900 ℃ in vacuum, immersing the obtained adsorbent into dilute hydrochloric acid for etching, taking out the adsorbent after no bubbles are generated in the dilute hydrochloric acid, and washing the adsorbent for 5 times by using clear water to remove the residual acid liquid in the adsorbent, thereby obtaining the capillary porous adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) Mixing the glucosamine hydrochloride solution obtained in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) of the embodiment according to the proportion of 14mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Example 5
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing micron-sized silicon dioxide powder with deionized water according to the proportion of 1g to 8mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) Mixing nano calcium carbonate powder with deionized water according to the proportion of 1g to 8mL, and uniformly stirring to prepare calcium carbonate suspension for later use.
(3) And (3) mixing the two suspensions prepared in the steps (1) and (2) according to the molar ratio of silicon dioxide to calcium carbonate of 6:1, and then carrying out ultrasonic stirring to obtain a mixed suspension.
(4) And (3) immersing the cellulose acetate cotton core into the mixed suspension obtained in the step (3) and carrying out ultrasonic vibration for 15min, then taking out the cellulose acetate cotton core, drying the cellulose acetate cotton core for 40min at 50 ℃, and repeating the step for three times.
(5) And (3) placing the cellulose acetate cotton core dried in the step (4) in a vacuum tube furnace, sintering the cellulose acetate cotton core in vacuum at 700 ℃ for 1h, immersing the obtained adsorbent into dilute sulfuric acid for etching, taking out the adsorbent after no bubbles are generated in the dilute sulfuric acid, and washing the adsorbent for 5 times by using clear water to remove the acid liquor remaining in the adsorbent, thereby obtaining the capillary porous adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) Mixing the hydrochloride glucosamine alcohol solution obtained in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) of the embodiment according to the proportion of 12mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2.5h, and filtering the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Example 6
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing micron-sized silicon dioxide powder with deionized water according to the proportion of 1g to 9mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) Mixing nano calcium carbonate powder with deionized water according to the proportion of 1g to 9mL, and uniformly stirring to prepare calcium carbonate suspension for later use.
(3) And (3) mixing the two suspensions prepared in the steps (1) and (2) according to the molar ratio of silicon dioxide to calcium carbonate of 4.5:1, and then carrying out ultrasonic stirring to obtain a mixed suspension.
(4) And (3) immersing the cellulose acetate cotton core into the mixed suspension obtained in the step (3) and carrying out ultrasonic vibration for 18min, then taking out the cellulose acetate cotton core, drying the cellulose acetate cotton core for 30min at the temperature of 55 ℃, and repeating the step for three times.
(5) And (3) placing the cellulose acetate cotton core dried in the step (4) in a vacuum tube furnace, sintering the cellulose acetate cotton core at 550 ℃ for 1.5h in vacuum, immersing the obtained adsorbent in acetic acid for etching, taking out the adsorbent after no bubbles are generated in the acetic acid, and washing the adsorbent for 5 times by using clear water to remove the acid liquor remaining in the adsorbent, thereby obtaining the capillary porous adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) Mixing the glucosamine hydrochloride solution obtained in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) of the embodiment according to the proportion of 10mL to 3g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering out the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Test example 1
A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) And (3) mixing the hydrochloride glucosamine solution obtained in the step (i) with an activated carbon adsorbent according to the proportion of 12mL to 5g, then adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering out the adsorbent to obtain an alcoholic solution containing glucosamine sulfate.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Test example 2
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing nano-scale silicon dioxide powder with deionized water according to the proportion of 1g to 10mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) Mixing nano calcium carbonate powder with deionized water according to the proportion of 1g to 10mL, and uniformly stirring to prepare calcium carbonate suspension for later use.
(3) And (3) mixing the two suspensions prepared in the steps (1) and (2) according to the molar ratio of the silicon dioxide to the calcium carbonate of 5:1, and then carrying out ultrasonic stirring to obtain a mixed suspension.
(4) And (3) immersing the cellulose acetate cotton core into the mixed suspension obtained in the step (3) and carrying out ultrasonic vibration for 15min, then taking out the cellulose acetate cotton core, drying for 45min at 50 ℃, and repeating the step for three times.
(5) And (3) placing the cellulose acetate cotton core dried in the step (4) in a vacuum tube furnace, sintering the cellulose acetate cotton core in vacuum at 650 ℃ for 1h, immersing the obtained adsorbent into dilute sulfuric acid for etching, taking out the adsorbent after no bubbles are generated in the dilute sulfuric acid, and washing the adsorbent for 3 times by using clear water to remove the acid liquor remaining in the adsorbent, thereby obtaining the capillary porous adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) Mixing the glucosamine hydrochloride solution obtained in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) of the embodiment according to the proportion of 12mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Test example 3
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing micron-sized silicon dioxide powder with deionized water according to the proportion of 1g to 10mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) Mixing nano calcium carbonate powder with deionized water according to the proportion of 1g to 10mL, and uniformly stirring to prepare calcium carbonate suspension for later use.
(3) And (3) mixing the two suspensions prepared in the steps (1) and (2) according to the molar ratio of the silicon dioxide to the calcium carbonate of 5:1, and then carrying out ultrasonic stirring to obtain a mixed suspension.
(4) And (3) immersing the cellulose acetate cotton core into the mixed suspension obtained in the step (3) and carrying out ultrasonic vibration for 15min, then taking out the cellulose acetate cotton core, drying for 45min at 50 ℃, and repeating the step for three times.
(5) And (4) placing the cellulose acetate cotton core dried in the step (4) into a vacuum tube furnace, and sintering for 1h at 650 ℃ in vacuum to obtain the capillary adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) Mixing the glucosamine hydrochloride solution obtained in the step (i) with the capillary adsorbent prepared in the step (5) of the embodiment according to the proportion of 12mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Test example 4
1. A preparation method of a porous tubular adsorbent comprises the following steps:
(1) mixing micron-sized silicon dioxide powder with deionized water according to the proportion of 1g to 10mL, and uniformly stirring to prepare silicon dioxide suspension for later use.
(2) And (2) immersing the cellulose acetate cotton core into the suspension obtained in the step (1) and carrying out ultrasonic vibration for 15min, then taking out the cellulose acetate cotton core, drying for 45min at 50 ℃, and repeating the step for three times.
(5) And (3) placing the cellulose acetate cotton core dried in the step (4) in a vacuum tube furnace, sintering the cellulose acetate cotton core in vacuum at 150 ℃ for 1h, immersing the obtained adsorbent into dilute sulfuric acid after the completion, taking out the adsorbent after the dilute sulfuric acid is unchanged, and washing the adsorbent for 3 times by using clear water to remove the acid liquor remaining in the adsorbent, thereby obtaining the capillary porous adsorbent.
2. A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and ethanol are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine solution is obtained.
(ii) Mixing the glucosamine hydrochloride solution obtained in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) of the embodiment according to the proportion of 12mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering the adsorbent to obtain the glucosamine sulfate-containing alcohol solution.
(iii) And (3) carrying out reduced pressure distillation on the alcoholic solution containing glucosamine sulfate in the step (ii), recovering the alcoholic solvent in the alcoholic solution, and obtaining a solid product, namely glucosamine sulfate.
Test example 5
A method for preparing glucosamine sulfate, comprising the steps of:
(i) the hydrochloride (sodium salt) glucosamine and water are mixed according to the proportion of 1g to 10ml, and the hydrochloride glucosamine aqueous solution is obtained.
(ii) And (3) mixing the aqueous solution of the glucosamine hydrochloride in the step (i) with the capillary-shaped porous adsorbent prepared in the step (5) in the example 1 according to the proportion of 12mL to 5g, adding a dilute sulfuric acid solution with the mass concentration of 33%, adsorbing for 2h, and filtering out the adsorbent to obtain an alcoholic solution containing the glucosamine sulfate.
(iii) (iii) drying the alcoholic solution containing glucosamine sulfate obtained in step (ii) to obtain a solid product, namely glucosamine sulfate.
The chloride ion content of glucosamine sulfate obtained in the above examples and test examples was measured by high performance liquid chromatography, and the results are shown in tables 1 and 2, respectively.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Content of chloride ions/wt. -%) | 0.086 | 0.074 | 0.082 | 0.088 | 0.079 | 0.071 |
TABLE 2
| Test example 1 | Test example 2 | Test example 3 | Test example 4 | Test example 5 | |
| Content of chloride ions/wt. -%) | 1.702 | 0.113 | 0.261 | 0.247 | 0.136 |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for preparing glucosamine sulfate is characterized by comprising the following steps:
(i) mixing the hydrochloride glucosamine and organic alcohol to obtain a hydrochloride glucosamine solution;
(ii) mixing the hydrochloride glucosamine alcohol solution with an adsorbent, then adding dilute sulfuric acid, and separating the adsorbent from the alcohol solution after adsorption to obtain an alcohol solution containing glucosamine sulfate;
(iii) removing the alcohol solvent in the alcoholic solution containing glucosamine sulfate to obtain glucosamine sulfate;
in step (ii), the preparation method of the adsorbent comprises the following steps:
(1) respectively dissolving micron-sized silicon dioxide powder and nano-sized calcium carbonate powder in a solvent to prepare suspension, and then mixing the two suspensions to obtain mixed suspension;
(2) immersing the cellulose acetate cotton core into the mixed suspension, then drying the cellulose acetate cotton core, and repeating the step (2) for at least three times;
(3) sintering the dried cellulose acetate cotton core under a vacuum condition, immersing the obtained adsorbent into acid liquor for etching after the sintering is finished, and then taking out the adsorbent to wash and remove residual acid liquor to obtain the cellulose acetate cotton core;
in the step (1), the proportion of the silicon dioxide, the calcium carbonate and the solvent is 1g: 8-12 mL; the solvent is deionized water or ethanol;
in the step (1), the molar ratio of silicon dioxide to calcium carbonate in the mixed suspension is 3-7: 1;
in the step (1), ultrasonically stirring the suspension;
in the step (2), immersing the cellulose acetate cotton core into the mixed suspension liquid and then carrying out ultrasonic vibration;
in the step (3), the sintering temperature is 550-900 ℃, and the time is 0.5-1.5 h;
in the step (3), the acid solution is any one of dilute sulfuric acid and acetic acid;
in the step (i), the alcoholic solution of hydrochloride glucosamine is a mixed solution of the hydrochloride glucosamine and any one of ethanol and propanol;
in the step (ii), the mixing ratio of the adsorbent to the hydrochloride glucosamine solution is 3-5 g: 10-15 mL.
2. The method for preparing glucosamine sulfate according to claim 1, wherein the drying temperature in step (2) is 45-60 ℃ for not less than 30 min.
3. The method for preparing glucosamine sulfate according to claim 1, wherein said acid solution is dilute sulfuric acid.
4. The process for preparing glucosamine sulfate according to any one of claims 1-3, wherein in step (ii), the separation method is centrifugation or filtration.
5. The process for preparing glucosamine sulfate according to any one of claims 1-3, wherein in step (iii), the solvent is removed by evaporation drying or distillation under reduced pressure.
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| CN210711306U (en) * | 2019-10-26 | 2020-06-09 | 刘晓勇 | Device for desalting sea sand by intelligently controlling silicon-calcium ratio to generate calcium silicate hydrate gel |
| CN112064423A (en) * | 2020-08-17 | 2020-12-11 | 浙江农林大学 | Preparation method of hydrated calcium silicate nanosheet, nano composite paper and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN210711306U (en) * | 2019-10-26 | 2020-06-09 | 刘晓勇 | Device for desalting sea sand by intelligently controlling silicon-calcium ratio to generate calcium silicate hydrate gel |
| CN112064423A (en) * | 2020-08-17 | 2020-12-11 | 浙江农林大学 | Preparation method of hydrated calcium silicate nanosheet, nano composite paper and preparation method thereof |
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| Title |
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| C一(A )·S-H对氯离子的吸附性能研究;万小梅等;《建筑材料学报》;20190228;第22卷(第1期);第31-37页 * |
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