CN103450289A - Preparation method of D-glucosamine hydrochloride - Google Patents

Abstract

The invention discloses a preparation method of D-glucosamine hydrochloride. That is to say, the citric acid waste residue obtained after the production of citric acid by fermentation is used as the raw material, and the mixed acid composed of hydrochloric acid and acetic acid is used as the hydrolysis reagent. After the steps of mixed acid hydrolysis, filtration, decolorization, suction filtration, crystallization, and drying, D - Glucosamine hydrochloride. The preparation method adopts the mixed acid composed of hydrochloric acid and acetic acid as the hydrolysis reagent in the hydrolysis reaction in the preparation process, thereby effectively reducing the consumption of hydrochloric acid when hydrolysis is carried out by hydrochloric acid alone, further reducing the corrosion degree to production equipment, and finally D- The yield of glucosamine hydrochloride reaches 5.0-5.2%. At the same time, the preparation method has the characteristics of abundant raw material resources, unlimited production resources and low production cost.

Description

A kind of preparation method of D-glucosamine hydrochloride

technical field

The technical field of the present invention is health care products and medical raw materials, and particularly relates to a method for preparing D-glucosamine hydrochloride using citric acid waste residue as raw material.

Background technique

Citric acid is a widely used organic acid. It can be used as a sour agent, a thickener, and a cleaning agent. It is widely used in food, beverage, pharmaceutical, chemical, detergent and other related industries. At present, my country is the world's largest exporter of citric acid, and most enterprises are currently producing citric acid by fermentation, and a large amount of citric acid waste residue is not properly utilized and is directly discharged.

D-glucosamine hydrochloride, molecular formula C ₆ H ₁₃ NO ₅ ·HCl, white crystal, odorless, slightly sweet, soluble in water, slightly soluble in methanol, insoluble in organic solvents such as ethanol. Glucosamine hydrochloride is the basic unit of many important polysaccharides in biological cells. It is an important precursor for the synthesis of bifidus factors. It has important physiological functions in organisms. It is mainly used for clinically enhancing the function of the human immune system and inhibiting cancer cells or fibers. The excessive growth of cells has certain medical effects on cancer and malignant tumors. At the same time, D-glucosamine hydrochloride is an intermediate of health care medicine that has emerged at home and abroad in recent years. It is also an important raw material for high-end cosmetic health care products. The active ingredient is also an additive of the latest third-generation health functional food.

At present, the raw materials used in the industrial production of glucosamine hydrochloride and its series derivatives are mainly chitin extracted from crustacean shells. This raw material is limited to coastal areas and is also greatly affected by seasons. The present invention adopts citric acid The waste residue is used as a raw material to obtain glucosamine hydrochloride through processes such as acid hydrolysis, filtration, decolorization, suction filtration, crystallization, and drying.

Before the present invention, there have been some invention patent disclosures about using citric acid waste residue to prepare glucosamine hydrochloride, such as CN200810088877.5, CN200810238484.8 and CN201010246930.7 and other patents. Although the CN201010246930.7 patent has broken through a misunderstanding before the first two patents, that is: the hydrolysis temperature cannot exceed 90°C, otherwise it will easily cause carbonization of citric acid slag, resulting in a decrease in production; but in this patent, the acid hydrolysis is completely used 30%~ 35% hydrochloric acid, so there are the following technical problems: one, hydrochloric acid is easy to volatilize, reacts violently in the process of heating and hydrolyzing, produces a large amount of acid mist, easily causes corrosion of reaction equipment, easily causes pollution to the environment, and post-treatment is also relatively difficult difficulty. In CN200810088877.5, the yield of citric acid waste residue with a water content lower than 18% is only 3-6%.

Contents of the invention

The purpose of the present invention is to provide a kind of preparation method of D-glucosamine hydrochloride in order to solve above-mentioned technical problem, and this preparation method promptly is raw material with the citric acid waste residue after the citric acid produced by fermentation method, is made up of hydrochloric acid and acetic acid The mixed acid is a hydrolysis reagent, and D-glucosamine hydrochloride is finally obtained through steps such as hydrolysis, filtration, decolorization, suction filtration, crystallization, and drying in sequence. The yield of D-glucosamine hydrochloride obtained by the preparation method is high, and at the same time, by adding acetic acid, the use of hydrochloric acid in acidolysis is reduced, the corrosion to production equipment is reduced, and the production cost is reduced.

Technical scheme of the present invention

A preparation method of D-glucosamine hydrochloride, that is, using the citric acid waste residue after the production of citric acid by fermentation as raw material, using the mixed acid composed of hydrochloric acid and acetic acid as the hydrolysis reagent, followed by hydrolysis, filtration, decolorization, extraction Steps such as filtration, crystallization, and drying finally obtain D-glucosamine hydrochloride, and its preparation process specifically includes the following steps:

(1), hydrolysis:

After mixing the citric acid waste residue with the mixed acid, control the stirring speed to 300-800r/min and the temperature to 80-100°C for 3-5 hours;

The amount of citric acid waste residue and mixed acid used above is calculated according to the mass volume ratio, that is, citric acid waste residue: mixed acid is 1g: 4 ~ 10mL;

The mixed acid is composed of hydrochloric acid and anhydrous acetic acid with a mass percentage of 30-38%, calculated by volume ratio, that is, hydrochloric acid with a mass percentage of 30-38%: anhydrous acetic acid mixed in a ratio of 1:1-2 become;

Described citric acid waste residue is the citric acid waste residue that moisture content is 20-30% fermentation factory produces citric acid gained;

(2), suction filtration:

After the reaction in step (1) is completed, the resulting reaction liquid is cooled to room temperature, and then suction filtered, and the obtained filter cake is washed with deionized water until the pH value of the eluate is 6.0 to 7.0, and the filtrate and eluate are combined to obtain Combined solution;

The above-mentioned combined solution is controlled on a rotary evaporator with a vacuum degree of 0.08-0.10MPa for vacuum distillation, and concentrated until the volume is reduced by half;

(3), decolorization:

Calculate the concentrated liquid and activated carbon obtained in step (2) according to the mass ratio, that is, the concentrated liquid: activated carbon ratio is 1:0.2~0.5, add activated carbon to the concentrated liquid obtained in step (2), and control the stirring speed to 300-800r /min, decolorization at 80-100°C for 2-5 hours;

(4), suction filtration:

Step (3) Cool to room temperature after decolorization, then suction filter, wash the obtained filter cake with deionized water until the eluate is neutral, combine the filtrate and eluate to obtain a combined liquid;

(5), crystallization:

Concentrate the combined liquid obtained in step (4) at a pressure of 0.08-0.10 MPa and a temperature of 50-80 ° C until the volume is concentrated to 10% to 20% of the original volume, stop heating, and add the liquid obtained in step (4) Combine 0.1-1 times the volume of absolute ethanol, gradually cool to room temperature, then crystallize at 0°C, refrigerate for 4-8 hours, filter, and rinse the crystals with absolute ethanol;

Then repeat the above-mentioned steps (3) and (4) to the crystallized filtrate to carry out multiple recrystallization until no more crystals can come out;

(6), drying:

All the crystals finally obtained in step (5) are dried under a controlled vacuum degree of 0.08-0.10 MPa and a temperature of 60-75° C. for 2-6 hours to obtain D-glucosamine hydrochloride.

Beneficial effects of the present invention

A kind of preparation method of D-glucosamine hydrochloride of the present invention, because the hydrolysis reaction in the preparation process adopts the mixed acid system of hydrochloric acid and acetic acid, thus effectively solves the problem of generating a large amount of acid mist during heating and hydrolysis when only using hydrochloric acid The problem is that the amount of hydrochloric acid used is reduced, and the degree of corrosion to production equipment is further reduced. Finally, the yield of D-glucosamine hydrochloride reaches 5.0-5.2%.

Further, the preparation method of a kind of D-glucosamine hydrochloride of the present invention is obtained by using the citric acid waste residue obtained from the production of citric acid in a fermentation plant as a raw material, and the resource is about to be recycled. At the same time, due to the abundant raw material resources, the production The resources are not limited, and the production cost is low, which further saves the cost of treating the environment, and has good social and economic benefits.

Detailed ways

The present invention is further illustrated below by specific examples, but the present invention is not limited.

Example 1

A preparation method of D-glucosamine hydrochloride, that is, using the citric acid waste residue after citric acid production by fermentation as a raw material, using a mixed acid composed of hydrochloric acid and acetic acid as a hydrolysis reagent, and successively undergoing hydrolysis, filtration, decolorization, and suction filtration , crystallization, drying and other steps to finally obtain D-glucosamine hydrochloride, and its preparation process specifically includes the following steps:

(1), hydrolysis:

Add 100g of citric acid waste residue with a moisture content of 20% into a 1000mL three-necked flask with a stirring device, add 800mL of mixed acid, control the stirring speed at 300r/min, and react at a temperature of 80°C for 3h;

The amount of citric acid waste residue and mixed acid with a moisture content of 20% used above is calculated by mass volume ratio, that is, citric acid waste residue with a moisture content of 20%: mixed acid is 1g: 4mL;

The mixed acid is calculated by volume ratio, that is, the mass percentage is 30% hydrochloric acid: anhydrous acetic acid is 1:1, and the mass percentage is 30% hydrochloric acid and anhydrous acetic acid, mixed;

Described moisture content is that the citric acid waste residue of 20% is that fermentation plant produces citric acid gain;

(2), suction filtration:

After (1) the reaction is completed, cool to room temperature, and then filter with suction to completely separate the solid and liquid, wash the obtained filter cake with deionized water until the pH value of the eluate is 7.0, combine the filtrate and eluate to obtain a combined solution , and then control the vacuum of the resulting combined solution to be 0.08 to 0.10 MPa for vacuum distillation, and concentrate until the volume is reduced by half;

(3), decolorization:

Transfer the concentrated solution obtained in step (2) to a 500mL three-necked flask with a stirring device, calculate the concentrated solution obtained in step (2) and activated carbon according to the mass ratio, that is, the concentrated solution: activated carbon The ratio is 1:0.2, in the step (2) Add activated carbon to the obtained concentrated solution, control the stirring speed to 800r/min, and decolorize at 100°C for 2 hours;

(4), suction filtration:

After (4) the decolorization is completed, cool to room temperature, then suction filter to completely separate the solid and liquid, wash the obtained filter cake with deionized water until the eluate is neutral, combine the filtrate and eluate to obtain the combined liquid;

(5), crystallization:

Transfer the combined liquid obtained in step (4) to a 500mL pear-shaped bottle, control the pressure at 0.10MPa, and concentrate at 65°C until the volume is concentrated to 12% of the original volume, and a large number of crystals appear, stop heating, and add as step ( 4) Add 0.1 times the volume of the combined liquid to absolute ethanol, gradually cool to room temperature, then crystallize at 0°C, refrigerate for 4 hours, filter, and rinse the crystals with absolute ethanol;

Then repeat the above-mentioned steps (3) and (4) for the filtrate after the above-mentioned crystallization to carry out multiple recrystallization until no more crystals can come out;

(6), drying:

All the final crystals obtained in step (5) were dried for 2 hours at a vacuum of 0.10 MPa and a temperature of 70° C. to obtain 5.1 g of D-glucosamine hydrochloride with a yield of 5.1%.

Example 2

A preparation method of D-glucosamine hydrochloride, that is, using the citric acid waste residue after citric acid production by fermentation as a raw material, using a mixed acid composed of hydrochloric acid and acetic acid as a hydrolysis reagent, and successively undergoing hydrolysis, filtration, decolorization, and suction filtration , crystallization, drying and other steps to finally obtain D-glucosamine hydrochloride, and its preparation process specifically includes the following steps:

(1), hydrolysis:

Add 100g of citric acid waste residue with a moisture content of 30% into a 1000mL three-necked flask with a stirring device, add 400mL of mixed acid, control the stirring speed at 500r/min, and react at a temperature of 100°C for 4h;

The amount of citric acid waste residue and mixed acid with a moisture content of 30% used above is calculated by mass volume ratio, that is, citric acid waste residue with a moisture content of 30%: mixed acid is 1g: 6mL;

The mixed acid is calculated by volume ratio, that is, hydrochloric acid with a mass percentage of 30%: anhydrous acetic acid is 1:2, which is formed by mixing hydrochloric acid and anhydrous acetic acid with a mass percentage of 30%;

Described moisture content is that the citric acid waste residue of 30% is that fermentation plant produces citric acid gain;

(2), suction filtration:

After (1) the reaction is completed, cool to room temperature, and then filter with suction to completely separate the solid and liquid, wash the obtained filter cake with deionized water until the pH value of the eluate is 6.0, combine the filtrate and eluate to obtain a combined solution , and then control the vacuum of the resulting combined solution to be 0.08 to 0.10 MPa for vacuum distillation, and concentrate until the volume is reduced by half;

(3), decolorization:

Transfer the concentrated solution obtained in step (2) to a 500mL three-necked flask with a stirring device, and calculate the concentrated solution obtained in step (2) and activated carbon according to the mass ratio, that is, the concentrated solution: The ratio of activated carbon is 1:0.5. (2) Add activated carbon to the obtained concentrated solution, control the stirring speed to 300r/min, and decolorize at 90°C for 2 hours;

(4), suction filtration:

After (3) the decolorization is completed, cool to room temperature, and then suction filter to completely separate the solid and liquid, wash the obtained filter cake with deionized water until the eluate is neutral, combine the filtrate and eluate to obtain the combined liquid;

(5), crystallization:

Transfer the above combined solution to a 500mL pear-shaped bottle, control the pressure at 0.09MPa, and concentrate at 50°C. When the volume is concentrated to 20% of the original volume, a large number of crystals appear, stop heating, and add the combined solution obtained in step (4). 1.0 times the volume of absolute ethanol, gradually cooled to room temperature, then crystallized at 0°C, refrigerated for 8 hours, filtered, and rinsed with absolute ethanol;

Then repeat the above steps (3) and (4) for the filtrate after crystallization to carry out multiple recrystallization until no more crystals can come out;

(6), drying:

All the final crystals obtained in step (5) were dried for 4 hours at a vacuum degree of 0.08 MPa and a temperature of 65° C. to obtain 5.20 g of D-glucosamine hydrochloride with a yield of 5.2%.

Example 3

A preparation method of D-glucosamine hydrochloride, that is, using the citric acid waste residue after citric acid production by fermentation as a raw material, using a mixed acid composed of hydrochloric acid and acetic acid as a hydrolysis reagent, and successively undergoing hydrolysis, filtration, decolorization, and suction filtration , crystallization, drying and other steps to finally obtain D-glucosamine hydrochloride, and its preparation process specifically includes the following steps:

(1), hydrolysis:

Add 200g of citric acid waste residue with a moisture content of 24% into a 1000mL three-necked flask with a stirring device, add 1000mL of mixed acid, control the stirring speed at 800r/min, and react at a temperature of 85°C for 5h;

The amount of 100-200g citric acid waste residue with a moisture content of 24% and the mixed acid used above is calculated according to the mass volume ratio, that is, 100-200g citric acid waste residue with a moisture content of 24%: mixed acid is 1g: 10mL;

The mixed acid is calculated by volume ratio, that is, the mass percentage is 38% hydrochloric acid: anhydrous acetic acid is 1:2, and the mass percentage is 38% hydrochloric acid and anhydrous acetic acid, mixed;

Described moisture content is that the citric acid waste residue of 24% is that fermentation plant produces citric acid gain;

(2), suction filtration:

After the reaction in step (1) is completed, cool to room temperature, and then suction filter to completely separate the solid and liquid, wash the obtained filter cake with deionized water until the pH value of the eluate is 7.0, combine the filtrate and eluate to obtain the combined liquid, and then control the vacuum degree of the resulting combined liquid to be 0.08～0.10MPa to carry out vacuum distillation, and concentrate until the volume is reduced by half;

(3), decolorization:

Transfer the concentrated solution of step (2) to a 500mL three-necked flask with a stirring device, calculate the concentrated solution obtained in step (2) and activated carbon according to the mass ratio, that is, the concentrated solution: activated carbon is 1:0.5 ratio, in step (2) ) Add activated carbon to the obtained concentrated solution, control the stirring speed to 600r/min, and decolorize at 100°C for 3h;

(4), suction filtration:

After the decolorization in step (3) is completed, cool to room temperature, and then suction filter to completely separate the solid and liquid, wash the obtained filter cake with deionized water until the eluate is neutral, combine the filtrate and eluate to obtain a combined liquid;

(5), crystallization:

Transfer the combined solution obtained in step (4) to a 500mL pear-shaped bottle, control the pressure at 0.08MPa, and concentrate at 80°C until the volume is concentrated to 20% of the original volume, and a large number of crystals appear, stop heating, and add as step ( 4) The resulting combined solution was mixed with 0.6 times the volume of absolute ethanol, gradually cooled to room temperature, then crystallized at 0°C, refrigerated for 6 hours, filtered, and the crystals were washed with absolute ethanol;

Then repeat the above steps (3) and (4) for the filtrate after crystallization to carry out multiple recrystallization until no more crystals can come out;

(6), drying:

All the final crystals obtained in step (5) were dried for 6 hours at a vacuum of 0.10 MPa and a temperature of 70° C. to obtain 5.00 g of D-glucosamine hydrochloride with a yield of 5.0%.

The results of the above-mentioned Examples 1 to 3 show that adding the mixed acid composed of hydrochloric acid-acetic acid can effectively reduce the consumption of hydrochloric acid, improve the acid mist phenomenon in production, and simplify the preparation process simultaneously, D-glucosamine salt The yield of acid salt can reach 5-5.2%.

The above content is only a basic description of the concept of the present invention, and any equivalent transformation made according to the technical solution of the present invention shall fall within the scope of protection of the present invention.

Claims (3)

1. a kind of preparation method of D-glucosamine hydrochloride, promptly produce the citric acid waste residue behind the citric acid with fermentation method as raw material, it is characterized in that with the mixed acid that hydrochloric acid and acetic acid are formed as hydrolysis reagent, the fermentation method production The citric acid waste residue after citric acid is successively hydrolyzed, filtered, decolorized with activated carbon, suction filtered, crystallized, and dried to finally obtain D-glucosamine hydrochloride. 2. the preparation method of a kind of D-glucosamine hydrochloride as claimed in claim 1 is characterized in that the mixed acid that described hydrochloric acid and acetic acid are formed, namely by mass percent is 30～38% hydrochloric acid and free Aqueous acetic acid, calculated by volume ratio, that is, hydrochloric acid with a mass percentage of 30-38%: anhydrous acetic acid mixed in a ratio of 1:1-2; The citric acid waste residue is the citric acid waste residue obtained from the production of citric acid in a fermentation plant with a moisture content of 20-30%. 3. the preparation method of a kind of D-glucosamine hydrochloride as claimed in claim 1 or 2 is characterized in that specifically comprising the following steps: (1) After mixing the citric acid waste residue with the mixed acid, control the stirring speed to 300-800r/min and the temperature to 80-100°C for 3-5 hours; The amount of the mixed acid formed by the above-mentioned citric acid waste residue, hydrochloric acid and anhydrous acetic acid is calculated by mass volume ratio, that is, citric acid waste residue: the mixed acid formed by hydrochloric acid and anhydrous acetic acid is 1g: 4 ~ 10mL; (2) After the reaction in step (1) is completed, cool the obtained reaction liquid to room temperature, then suction filter, and wash the obtained filter cake with deionized water until the pH value of the eluate is 6-7, combine the filtrate and wash liquid out to obtain the combined liquid; The above-mentioned combined solution is controlled on a rotary evaporator with a vacuum degree of 0.08-0.10MPa for vacuum distillation, and concentrated until the volume is reduced by half; (3) Calculate the concentrated solution and activated carbon obtained in step (2) according to the mass ratio, that is, the concentrated solution:activated carbon ratio is 1:0.2~0.5, and the stirring speed is controlled at 300-800r/min, and the temperature is 80~100°C Carry out decolorization for 2 to 5 hours; (4), step (3) After decolorization, cool to room temperature, then suction filter, wash the obtained filter cake with deionized water until the eluate is neutral, combine the filtrate and eluate to obtain the combined liquid; (5) Concentrate the combined solution obtained in step (4) with a vacuum degree of 0.08-0.10 MPa and a temperature of 50-80°C until the volume is concentrated to 10%-20% of the original volume, stop heating, and add (4) The resulting combined solution was dehydrated with 0.1-1.0 times the volume of ethanol, gradually cooled to room temperature, then crystallized at 0°C, refrigerated for 4-8 hours, filtered, and washed with dehydrated ethanol; Then repeat the above-mentioned steps (3) and (4) to the above-mentioned crystallized filtrate to carry out multiple recrystallization until no more crystals can come out; (6) All the crystals finally obtained in step (5) are vacuum-dried at a vacuum degree of 0.08-0.10 MPa and a temperature of 60-75° C. to obtain D-glucosamine hydrochloride.