CN118389625A - Method for co-producing glucosamine hydrochloride and D-psicose from fructose solution - Google Patents

Abstract

The invention discloses a method for co-producing glucosamine hydrochloride and D-psicose from a fructose solution, and relates to the technical field of psicose production, wherein D-psicose 3-epimerase is added to the fructose solution to obtain a mixed solution containing fructose and psicose, and the mixed solution is further added with glucosamine-6-phosphate synthase and ammonium chloride to obtain a feed solution containing glucosamine and psicose, and then a ceramic membrane, an ultrafiltration membrane, a cation resin column, and a nanofiltration membrane are introduced, and then the mixture is concentrated by heat, cooled, and filtered to obtain psicose, and then hydrochloric acid is used as a desorbent to rinse the cation exchange resin column, and a desorbent with a pH of 2-3 is collected, concentrated, cooled, and filtered to obtain a crude glucosamine hydrochloride product, and the crude product is dissolved in water, decolorized, and cooled and filtered to obtain a finished glucosamine hydrochloride product. Time and economic costs are saved, enzyme inactivation and multi-stage decolorization are not required, and the product purity is high and there are few by-products.

Description

A method for co-producing glucosamine hydrochloride and D-psicose from fructose solution

Technical Field

The invention relates to the technical field of psicose production, and in particular to a method for co-producing glucosamine hydrochloride and D-psicose from a fructose solution.

Background technique

D-psicose is a very important rare ketohexose with a sweetness of 70% of sucrose, but almost zero energy. Its solvent properties and taste are similar to those of sucrose, and it can undergo the Maillard reaction. In the food and drug industry, D-psicose is an ideal substitute for sucrose. In addition, D-psicose has the functions of inhibiting obesity, lowering blood sugar, and lowering blood lipids. It is very suitable for consumption by diabetic patients and obese people, so it has significant effects in medical treatment and health care. At present, the production of D-psicose is mainly based on the isomerization reaction of D-fructose catalyzed by isomerase. This reaction is a reversible reaction with a low conversion rate of about 30%.

Glucosamine hydrochloride is also known as 2-amino-2-deoxy-glucose hydrochloride, and its molecular formula is C ₆ H ₁₃ NO ₅ .HCl. Glucosamine can stimulate mucopolysaccharide synthesis and increase the intake of bone calcium in the human body, improve and enhance the viscosity of synovial fluid, increase synovial fluid synthesis, thereby improving joint lubrication function, helping to improve joint mobility and relieve joint pain. At present, the traditional production methods of glucosamine hydrochloride at home and abroad include biological extraction and chemical synthesis, among which biological extraction is the main production method. The biological extraction method refers to first extracting chitin or chitosan from shrimp and crab shells, and then hydrolyzing it with hydrochloric acid to form glucosamine hydrochloride. The defects of this production method mainly include: first, glucosamine hydrochloride extracted from aquatic product shells is not suitable for patients with allergic reactions to aquatic products; second, the purification process is complicated, the product has a fishy smell and is unstable; third, affected by environmental pollution, glucosamine hydrochloride extracted from shrimp and crab shells is inevitably contaminated by heavy metals. In comparison, the production of glucosamine hydrochloride by microbial fermentation in the biological extraction method is a better process route, and the products produced by the microbial fermentation method have no fishy smell and are not limited by production resources; the use of metabolic engineering to improve strains can obtain engineered bacteria with extremely high yields, which have the potential for large-scale industrial production. However, the genetic modification of microbial metabolic pathways is difficult, and there are disadvantages such as the difficulty in controlling the genetic stability of engineered strains and the easy production of metabolic byproducts, which affects industrial applications and increases production costs.

Summary of the invention

The technical problem to be solved by the present invention is: in view of the shortcomings of the prior art, a method for co-producing glucosamine hydrochloride and D-psicose from a fructose solution is provided, wherein the product has high purity and few by-products.

In order to solve the above technical problems, the technical solution of the present invention is:

A method for co-producing glucosamine hydrochloride and D-psicose from a fructose solution comprises the following steps:

A: D-psicose 3-epimerase is added to the fructose solution, and then the first buffer solution is added to adjust the pH of the system to 6-8, and the reaction is carried out at 30-40° C. for 4-10 hours to obtain a reaction solution;

B: The reaction solution enters the hollow fiber membrane for separation to achieve separation of the enzyme and the mixed solution;

C: adding glucosamine-6-phosphate synthase and ammonium chloride to the mixed solution, mixing evenly, then adding the second buffer solution to adjust the pH of the system to 6.5-7.5, reacting at 30-50° C. for 8-14 hours, and obtaining a feed solution containing glucosamine and D-psicose;

D: filtering the liquid containing glucosamine and allulose through a ceramic membrane, and collecting the ceramic membrane clear liquid;

E: passing the ceramic membrane clear liquid through the ultrafiltration membrane and collecting the ultrafiltration membrane clear liquid;

F: The collected ultrafiltration membrane clear liquid is fed into a cation exchange resin column, and the collected first effluent is fed into an anion exchange resin column to collect a second effluent;

G: filtering the second effluent through a nanofiltration membrane and collecting the nanofiltration concentrate;

H: Concentrating the nanofiltrate concentrate to a solid content of 70-80% w/w at a temperature of 50-70° C. and a vacuum degree of <-0.090 MPa, then cooling to 10-15° C., filtering with suction, washing with ethanol, and filtering with suction to obtain D-psicose;

I: Then, the hydrochloric acid solution is passed through the cation exchange resin column in step F, and the effluent at pH 2-3 is collected and concentrated to a solid content of 70-90% w/w, and then cooled to 20-25°C at a rate of 1-5°C/h, and filtered to obtain a crude product of glucosamine hydrochloride.

Preferably, the concentration of the fructose solution is 50-100 g/L, the amount of D-psicose 3-epimerase added is 10-30 U/mL, and the amount of glucosamine-6-phosphate synthase added is 30-50 U/mL.

Preferably, the first buffer solution and the second buffer solution are both phosphate buffer solutions, and the concentrations of the first buffer solution and the second buffer solution are both 50-100 mmol/L.

Preferably, the feed flow rate of the hollow fiber membrane is 30-40 mL/min.

Preferably, the amount of ammonium chloride added is 200-800 mmol/L of the volume of the mixed solution.

Preferably, the pore size range of the ceramic membrane is 20-100 nm, the pore size range of the ultrafiltration membrane is 5000-10000 Da, and the pore size range of the nanofiltration membrane is 150-300 Da.

Preferably, in step F, the feed flow rate of the cation exchange resin column is 1-5 BV/h, and the feed flow rate of the anion exchange resin column is 0.5-1.5 BV/h;

The concentration of the hydrochloric acid solution in step I is 0.1-0.5 mol/L, the amount added is 2-3 times the volume of the cation exchange resin column, and the flow rate is 0.5-1.5 BV/h;

The anion exchange resin column is regenerated by adding sodium hydroxide solution.

Preferably, in step I, the effluent with a pH value less than 2 is collected and used for preparing the hydrochloric acid solution;

The nanofiltration clear liquid in step G is used for the preparation of hydrochloric acid solution and sodium hydroxide solution.

Preferably, pure water is added to the crude glucosamine hydrochloride, stirred, heated until the crude product is dissolved, activated carbon is added for decolorization, then cooled, filtered, washed, and dried to obtain the finished glucosamine phosphate.

Preferably, the amount of purified water added is 1-3 times the weight of the crude glucosamine hydrochloride, the stirring speed after adding purified water is 50-150r/min, and the heating and dissolving temperature is 50-80°C;

The amount of activated carbon added is 1-5% w/w of the weight of the crude glucosamine hydrochloride, and the temperature is lowered to 20-25° C. after decolorization.

Due to the adoption of the above technical solution, the beneficial effects of the present invention are:

1. The enzyme and the liquid are separated by hollow fiber membrane and ceramic membrane, without the need for simulated moving bed, which improves the separation efficiency and saves production costs.

2. Through D-psicose 3-epimerase and glucosamine-6-phosphate synthase, the conversion of fructose is more thorough, which improves the utilization rate of fructose, avoids the waste of raw materials, and improves the yield of the product.

3. By co-producing D-psicose and glucosamine hydrochloride, time and production costs are saved and the economic benefits of the enterprise are improved.

4. No enzyme inactivation and multi-stage decolorization are required, which simplifies the production steps and makes the process simpler.

5. The obtained glucosamine hydrochloride and D-psicose products have high purity and few by-products.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a liquid chromatogram of glucosamine hydrochloride in Example 3 of the present invention;

FIG. 2 is a liquid chromatogram of D-psicose in Example 3 of the present invention.

Detailed ways

The present invention will be further described below in conjunction with the embodiments.

Example 1

A method for co-producing glucosamine hydrochloride and D-psicose from a fructose solution comprises the following steps:

A: D-psicose 3-epimerase was added to a 50 g/L fructose solution (50 L), and then a 50 mmol/L phosphate buffer solution (the concentration of dipotassium hydrogen phosphate was 8.71 g/L, and the concentration of potassium dihydrogen phosphate was 0.68 g/L) was added to adjust the pH of the system to 6, and the mixture was reacted at 30° C. for 10 h to obtain a reaction solution (52.0 L), wherein the amount of D-psicose 3-epimerase added was 10 U/mL;

B: The reaction solution was separated by hollow fiber membrane at a flow rate of 30 mL/min to achieve separation of enzyme and mixed solution (55.0 L);

C: Add glucosamine-6-phosphate synthase and ammonium chloride to the mixed solution, mix well, then add 50 mmol/L phosphate buffer solution (the concentration of dipotassium hydrogen phosphate is 8.71 g/L, the concentration of potassium dihydrogen phosphate is 0.68 g/L) to adjust the pH of the system to 6.5, react at 30°C for 14 hours, and obtain a feed solution (64.0 L) containing glucosamine and D-psicose, wherein the amount of glucosamine-6-phosphate synthase added is 30 U/mL, and the amount of ammonium chloride added accounts for 200 mmol/L of the volume of the mixed solution;

D: filtering the slurry containing glucosamine and psicose through a ceramic membrane, and collecting the ceramic membrane clear liquid (68.0 L), wherein the pore size range of the ceramic membrane is 100 nm;

E: passing the ceramic membrane clear liquid through an ultrafiltration membrane, and collecting the ultrafiltration membrane clear liquid (76.0 L), wherein the pore size range of the ultrafiltration membrane is 10000 Da;

F: The collected ultrafiltration membrane clear liquid is fed into a cation exchange resin column at a flow rate of 1 BV/h, and the collected first effluent (96.0 L) is fed into an anion exchange resin column at a flow rate of 0.5 BV/h to collect a second effluent (116.0 L);

G: filtering the second effluent through a nanofiltration membrane, collecting the nanofiltration concentrate (13.5 L), wherein the pore size range of the nanofiltration membrane is 300 Da, and the nanofiltration clear solution (86.5 L) is used for the preparation of hydrochloric acid solution and sodium hydroxide solution;

H: The nanofiltrate concentrate was concentrated to a solid content of 70% w/w at a temperature of 50° C. and a vacuum degree of <-0.090 MPa, then cooled to 10° C., filtered, washed with ethanol, and filtered to obtain D-psicose (638.0 g) with a yield of 85.1% and a purity of 99.3%. The crystal color was white;

I: Then, 0.1 mol/L hydrochloric acid solution was fed into the cation exchange resin column in step F at a flow rate of 0.5 BV/h, and the feed amount of the hydrochloric acid solution was twice the volume of the cation exchange resin column. The effluent (14 L) with a pH value less than 2 was collected and used for the preparation of the hydrochloric acid solution, and the effluent (30 L) with a pH value of 2-3 was collected and concentrated to a solid content of 70% w/w, and then cooled to 25°C at a rate of 5°C/h, and filtered to obtain a crude glucosamine hydrochloride product (1513 g).

Pure water was added to the crude glucosamine hydrochloride, stirred, and heated until the crude product was dissolved (6.5 L). Activated carbon was added for decolorization, and then cooled, filtered, washed, and dried to obtain the finished glucosamine phosphate (1301 g) with a yield of 86.0%, a purity of 99.1%, and white crystal color.

The amount of purified water added is 3 times the weight of the crude glucosamine hydrochloride, the stirring speed after adding purified water is 50r/min, and the heating and dissolving temperature is 50°C;

The amount of activated carbon added is 1% w/w of the weight of the crude glucosamine hydrochloride, and the temperature is lowered to 20° C. after decolorization.

The anion exchange resin column is regenerated by adding sodium hydroxide solution.

Example 2

A method for co-producing glucosamine hydrochloride and D-psicose from a fructose solution comprises the following steps:

A: D-psicose 3-epimerase was added to a 100 g/L fructose solution (50.0 L), and then a phosphate buffer solution with a concentration of 100 mmol/L (the concentration of dipotassium hydrogen phosphate was 15.66 g/L, and the concentration of potassium dihydrogen phosphate was 1.36 g/L) was added to adjust the pH of the system to 8, and the reaction was carried out at 40° C. for 4 h to obtain a reaction solution (60.0 L), wherein the amount of D-psicose 3-epimerase added was 30 U/mL;

B: The reaction solution was separated by hollow fiber membrane at a flow rate of 40 mL/min to achieve separation of enzyme and mixed solution (65.0 L);

C: Add glucosamine-6-phosphate synthase and ammonium chloride to the mixed solution, mix well, then add 100 mmol/L phosphate buffer solution (the concentration of dipotassium hydrogen phosphate is 15.66 g/L, and the concentration of potassium dihydrogen phosphate is 1.36 g/L) to adjust the pH of the system to 7.5, react at 50°C for 8 hours, and obtain a feed solution (75.5 L) containing glucosamine and D-psicose, wherein the amount of glucosamine-6-phosphate synthase added is 50 U/mL, and the amount of ammonium chloride added accounts for 800 mmol/L of the volume of the mixed solution;

D: filtering the slurry containing glucosamine and psicose through a ceramic membrane, and collecting the ceramic membrane clear liquid (86.0 L), wherein the pore size range of the ceramic membrane is 20 nm;

E: passing the ceramic membrane clear liquid through an ultrafiltration membrane, and collecting the ultrafiltration membrane clear liquid (92.0 L), wherein the pore size range of the ultrafiltration membrane is 5000 Da;

F: The collected ultrafiltration membrane clear liquid is fed into a cation exchange resin column at a flow rate of 5 BV/h, and the collected first effluent (112 L) is fed into an anion exchange resin column at a flow rate of 1.5 BV/h to collect a second effluent (132 L);

G: Filter the second effluent through a nanofiltration membrane, collect the nanofiltration concentrate (17.6 L), the pore size range of the nanofiltration membrane is 150 Da, and the nanofiltration clear liquid (124.0 L) is used for the preparation of hydrochloric acid solution and sodium hydroxide solution;

H: The nanofiltrate concentrate was concentrated to a solid content of 80% w/w at a temperature of 70° C. and a vacuum degree of <-0.090 MPa, then cooled to 15° C., filtered, washed with ethanol, and filtered to obtain D-psicose (1329.5 g) with a yield of 88.6% and a purity of 99.5%. The crystal color was white;

I: Then, 0.5 mol/L hydrochloric acid solution was fed into the cation exchange resin column in step F at a flow rate of 1.5 BV/h, and the feed amount of the hydrochloric acid solution was 3 times the volume of the cation exchange resin column. The effluent (16.0 L) with a pH value less than 2 was collected and used for the preparation of the hydrochloric acid solution, and the effluent (46.0 L) with a pH value of 2-3 was collected and concentrated to a solid content of 90% w/w, and then cooled to 20°C at a rate of 1°C/h, and filtered to obtain a crude product of glucosamine hydrochloride (3150 g).

Add pure water to the crude glucosamine hydrochloride, stir, heat until the crude product is dissolved (11.0L), add activated carbon for decolorization, then cool, filter, wash, and dry to obtain the finished glucosamine phosphate (2914g) with a yield of 92.5%, a purity of 99.4%, and white crystal color.

The amount of purified water added is twice the weight of the crude glucosamine hydrochloride, the stirring speed after adding purified water is 150r/min, and the heating and dissolving temperature is 65°C;

The amount of activated carbon added is 5% w/w of the weight of the crude glucosamine hydrochloride, and the temperature is lowered to 25° C. after decolorization.

The anion exchange resin column is regenerated by adding sodium hydroxide solution.

Example 3

A method for co-producing glucosamine hydrochloride and D-psicose from a fructose solution comprises the following steps:

A: D-psicose 3-epimerase was added to 80 g/L fructose solution (50.0 L), and then 80 mmol/L phosphate buffer solution (the concentration of dipotassium hydrogen phosphate was 13.93 g/L, and the concentration of potassium dihydrogen phosphate was 1.09 g/L) was added to adjust the pH of the system to 7.5, and the mixture was reacted at 35° C. for 8 h to obtain a reaction solution (55.0 L), wherein the amount of D-psicose 3-epimerase added was 20 U/mL;

B: The reaction solution was separated by hollow fiber membrane at a flow rate of 35 mL/min to achieve separation of enzyme and mixed solution (58.0 L);

C: Add glucosamine-6-phosphate synthase and ammonium chloride to the mixed solution, mix well, then add phosphate buffer solution with a concentration of 80 mmol/L (the concentration of dipotassium hydrogen phosphate is 13.93 g/L, and the concentration of potassium dihydrogen phosphate is 1.09 g/L) to adjust the pH of the system to 7.0, react at 40°C for 10 hours, and obtain a feed solution (68.0 L) containing glucosamine and D-psicose, wherein the amount of glucosamine-6-phosphate synthase added is 40 U/mL, and the amount of ammonium chloride added accounts for 600 mmol/L of the volume of the mixed solution;

D: filtering the slurry containing glucosamine and psicose through a ceramic membrane, and collecting the ceramic membrane clear liquid (73.0 L), wherein the pore size range of the ceramic membrane is 80 nm;

E: passing the ceramic membrane clear liquid through an ultrafiltration membrane, and collecting the ultrafiltration membrane clear liquid (78.0 L), wherein the pore size range of the ultrafiltration membrane is 8000 Da;

F: The collected ultrafiltration membrane clear liquid is fed into a cation exchange resin column at a flow rate of 3 BV/h, and the collected first effluent (109.5 L) is fed into an anion exchange resin column at a flow rate of 1 BV/h to collect a second effluent (129.5 L);

G: Filter the second effluent through a nanofiltration membrane, collect the nanofiltration concentrate (14.5 L), the pore size range of the nanofiltration membrane is 200 Da, and the nanofiltration clear liquid (125.0 L) is used for the preparation of hydrochloric acid solution and sodium hydroxide solution;

H: The nanofiltrate concentrate was concentrated to a solid content of 75% w/w at a temperature of 60° C. and a vacuum degree of <-0.090 MPa, then cooled to 12° C., filtered, washed with ethanol, and filtered to obtain D-psicose (1134 g) with a yield of 94.5 and a purity of 99.8%. The crystal color was white;

I: Then, 0.3 mol/L hydrochloric acid solution was fed into the cation exchange resin column in step F at a flow rate of 1.2 BV/h, and the feed amount of the hydrochloric acid solution was 2.5 times the volume of the cation exchange resin column. The effluent (15 L) with a pH value less than 2 was collected for the preparation of the hydrochloric acid solution, and the effluent (40.5 L) with a pH value of 2-3 was collected and concentrated to a solid content of 80% w/w, and then cooled to 22°C at a rate of 3°C/h, and filtered to obtain a crude product of glucosamine hydrochloride (2562 g).

Pure water was added to the crude glucosamine hydrochloride, stirred, and heated until the crude product was dissolved (6.5 L). Activated carbon was added for decolorization, and then cooled, filtered, washed, and dried to obtain the finished glucosamine phosphate (2421 g) with a yield of 94.5%, a purity of 99.6%, and white crystal color.

The amount of purified water added is 1 times the weight of the crude glucosamine hydrochloride. The stirring speed after adding purified water is 100 r/min, and the heating and dissolving temperature is 80°C.

The amount of activated carbon added is 3% w/w of the weight of the crude glucosamine hydrochloride, and the temperature is lowered to 22° C. after decolorization.

The anion exchange resin column is regenerated by adding sodium hydroxide solution.

Comparative Example 1

A method for producing D-psicose from a fructose solution, comprising the following steps:

A: D-psicose 3-epimerase was added to 80 g/L fructose solution (50.0 L), and then 80 mmol/L phosphate buffer solution (the concentration of dipotassium hydrogen phosphate was 13.93 g/L, and the concentration of potassium dihydrogen phosphate was 1.09 g/L) was added to adjust the pH of the system to 7.5, and the mixture was reacted at 35° C. for 8 h to obtain a reaction solution (56.0 L), wherein the amount of D-psicose 3-epimerase added was 20 U/mL;

B: The reaction solution was separated by a hollow fiber membrane at a flow rate of 35 mL/min to achieve separation of the enzyme and the D-psicose-containing liquid (61.0 L);

C: Passing the D-psicose-containing liquid through an ultrafiltration membrane, and collecting the ultrafiltration membrane clear liquid (71.0 L), wherein the pore size range of the ultrafiltration membrane is 8000 Da;

D: The collected ultrafiltration membrane clear liquid was passed into an anion exchange resin column at a flow rate of 1 BV/h, and the effluent (92.5 L) was collected;

E: Filter the effluent through a nanofiltration membrane with a pore size range of 200 Da to collect the nanofiltration concentrate (11.6 L);

F: The nanofiltrate concentrate was concentrated to a solid content of 75% w/w at a temperature of 60° C. and a vacuum degree of <-0.090 MPa, then cooled to 12° C., filtered, washed with ethanol, and filtered to obtain D-psicose (942 g) with a yield of 78.5%, a purity of 99.0%, and white crystal color.

Comparative Example 2

A method for producing glucosamine hydrochloride from a fructose solution comprises the following steps:

A: Add glucosamine-6-phosphate synthase and ammonium chloride to 80 g/L fructose solution (50 L), mix well, then add phosphate buffer solution with a concentration of 80 mmol/L (the concentration of dipotassium hydrogen phosphate is 13.93 g/L, and the concentration of potassium dihydrogen phosphate is 1.09 g/L) to adjust the pH of the system to 7.0, react at 40°C for 10 h, and obtain a glucosamine-containing liquid (58.5 L), wherein the amount of glucosamine-6-phosphate synthase added is 40 U/mL, and the amount of ammonium chloride added accounts for 600 mmol/L of the volume of the mixed solution;

D: filtering the glucosamine-containing liquid through a ceramic membrane, collecting the ceramic membrane clear liquid (69.0 L), wherein the pore size range of the ceramic membrane is 80 nm;

E: passing the ceramic membrane clear liquid through an ultrafiltration membrane, and collecting the ultrafiltration membrane clear liquid (80.0 L), wherein the pore size range of the ultrafiltration membrane is 8000 Da;

F: The collected ultrafiltration membrane clear liquid was passed into a cation exchange resin column at a flow rate of 3 BV/h, and the effluent (102.5 L) was collected;

G: Filter the effluent through a nanofiltration membrane with a pore size range of 200 Da to collect the nanofiltration concentrate (13.4 L);

H: Then, 0.3 mol/L hydrochloric acid solution was fed into the cation exchange resin column in step F at a flow rate of 1.2 BV/h, and the feed amount of the hydrochloric acid solution was 2.5 times the volume of the cation exchange resin column. The effluent (16.0 L) with a pH value less than 2 was collected for the preparation of the hydrochloric acid solution, and the effluent (45.0 L) with a pH value of 2-3 was collected and concentrated to a solid content of 80% w/w, and then cooled to 22°C at a rate of 3°C/h, and filtered to obtain a crude glucosamine hydrochloride product (2310 g).

Pure water was added to the crude glucosamine hydrochloride, stirred, and heated until the crude product was dissolved (8.5 L). Activated carbon was added for decolorization, and then cooled, filtered, washed, and dried to obtain the finished glucosamine phosphate (1767 g) with a yield of 76.5%, a purity of 98.7%, and white crystals.

The amount of purified water added is twice the weight of the crude glucosamine hydrochloride. The stirring speed after adding purified water is 100 r/min, and the heating and dissolving temperature is 70°C.

The amount of activated carbon added is 3% w/w of the weight of the crude glucosamine hydrochloride, and the temperature is lowered to 22° C. after decolorization.

The anion exchange resin column is regenerated by adding sodium hydroxide solution.

It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope limited by the appended claims of the application.

Claims (10)

1. A method for co-producing glucosamine hydrochloride and D-psicose from a fructose solution, comprising the steps of:

A: adding D-psicose 3-epimerase into the fructose solution, then adding a first buffer solution to adjust the pH of the system to 6-8, and reacting for 4-10 hours at 30-40 ℃ to obtain a reaction solution;

B: separating the reaction liquid by a hollow fiber membrane to realize the separation of enzyme and mixed liquid;

C: adding glucosamine-6-phosphate synthetase and ammonium chloride into the mixed solution, uniformly mixing, adding a second buffer solution to adjust the pH of the system to 6.5-7.5, and reacting at 30-50 ℃ for 8-14h to obtain a feed liquid containing glucosamine and D-psicose;

D: filtering feed liquid containing glucosamine and psicose by a ceramic membrane, and collecting clear liquid of the ceramic membrane;

E: passing the ceramic membrane clear liquid through an ultrafiltration membrane, and collecting the ultrafiltration membrane clear liquid;

F: feeding the collected ultrafiltration membrane clear liquid into a cation exchange resin column, feeding the collected first effluent into an anion exchange resin column, and collecting to obtain a second effluent;

g: filtering the second effluent through a nanofiltration membrane, and collecting nanofiltration concentrated solution;

H: concentrating the nanofiltration concentrated solution at 50-70deg.C and vacuum degree of < -0.090Mpa until the solid content is 70-80% w/w, cooling to 10-15deg.C, vacuum filtering, washing with ethanol, and vacuum filtering to obtain D-psicose;

I: and then, using hydrochloric acid solution to enter a cation exchange resin column in the step F, collecting effluent liquid with the pH of 2-3, concentrating until the solid content is 70-90% w/w, cooling to 20-25 ℃ at the speed of 1-5 ℃/h, and filtering to obtain a glucosamine hydrochloride crude product.

2. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 1, wherein: the concentration of the fructose solution is 50-100g/L, the addition amount of the D-psicose 3-epimerase is 10-30U/mL, and the addition amount of the glucosamine-6-phosphate synthase is 30-50U/mL.

3. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 1, wherein: the first buffer solution and the second buffer solution are phosphate buffer solutions, and the concentrations of the first buffer solution and the second buffer solution are 50-100mmol/L.

4. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 1, wherein: the feeding flow rate of the hollow fiber membrane is 30-40mL/min.

5. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 1, wherein: the addition amount of the ammonium chloride accounts for 200-800mmol/L of the volume of the mixed solution.

6. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 1, wherein: the pore diameter of the ceramic membrane ranges from 20 nm to 100nm, the pore diameter of the ultrafiltration membrane ranges from 5000 Da to 10000Da, and the pore diameter of the nanofiltration membrane ranges from 150 Da to 300Da.

7. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 1, wherein: the feeding flow rate of the cation exchange resin column in the step F is 1-5BV/h, and the feeding flow rate of the anion exchange resin column is 0.5-1.5BV/h;

The concentration of the hydrochloric acid solution in the step I is 0.1-0.5mol/L, the adding amount is 2-3 times of the volume of the cation exchange resin column, and the flow rate is 0.5-1.5BV/h;

the anion exchange resin column is added with sodium hydroxide solution for regeneration.

8. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 1, wherein: the effluent with the pH less than 2 is collected in the step I and is used for preparing hydrochloric acid solution;

the nanofiltration solution in the step G is used for preparing hydrochloric acid solution and sodium hydroxide solution.

9. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 1, wherein: adding pure water into the glucosamine hydrochloride crude product, stirring, heating to dissolve the crude product, adding active carbon for decoloring, cooling, filtering, washing and drying to obtain a glucosamine phosphate finished product.

10. A process for co-producing glucosamine hydrochloride and D-psicose from a fructose solution as set forth in claim 9, wherein: the adding amount of the purified water is 1-3 times of the weight of the crude glucosamine hydrochloride, the stirring speed after adding the purified water is 50-150r/min, and the heating and dissolving temperature is 50-80 ℃;

The addition amount of the activated carbon accounts for 1-5% w/w of the weight of the crude glucosamine hydrochloride, and the temperature is reduced to 20-25 ℃ after decolorization.