CN114028949A - Boron removal method for isomerized lactose liquid - Google Patents

Boron removal method for isomerized lactose liquid Download PDF

Info

Publication number
CN114028949A
CN114028949A CN202111527595.2A CN202111527595A CN114028949A CN 114028949 A CN114028949 A CN 114028949A CN 202111527595 A CN202111527595 A CN 202111527595A CN 114028949 A CN114028949 A CN 114028949A
Authority
CN
China
Prior art keywords
boron
boric acid
isomerized lactose
lactose
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111527595.2A
Other languages
Chinese (zh)
Inventor
秦士恒
刘建
任尚美
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Jianyihong Biopharmaceutical Co ltd
Original Assignee
Shandong Jianyihong Biopharmaceutical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Jianyihong Biopharmaceutical Co ltd filed Critical Shandong Jianyihong Biopharmaceutical Co ltd
Priority to CN202111527595.2A priority Critical patent/CN114028949A/en
Publication of CN114028949A publication Critical patent/CN114028949A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422Electrodialysis
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/30Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08Selective adsorption, e.g. chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027Nanofiltration

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • Nutrition Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Urology & Nephrology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a boron removal method of an isomerized lactose liquid, which relates to the technical field of isomerized lactose preparation methods, and adopts the technical scheme that the method comprises the following steps: adding boric acid into a lactose solution with a certain concentration, adjusting the pH value to 10.0-12.0 by adopting an alkali solution, and then reacting at a high temperature to obtain a crude isomerized lactose liquid; recovering an alkali solution by an electrodialysis method: passing the crude isomerized lactose liquid through an anode chamber of electrodialysis, wherein isomerized lactose liquid and boric acid are obtained in the anode chamber, and an alkali solution is obtained in a cathode chamber; removing boron by using a nanofiltration membrane: removing boric acid from the anolyte by adopting a nanofiltration membrane to obtain trapped fluid and permeate, wherein the trapped fluid is mainly isomerized lactose, and the permeate is boric acid; and removing boron from the boron-removing resin. The invention has the beneficial effects that: the boric acid and the alkali solution added in the production process are recycled and reused, so that the production cost is reduced, the emission of boron-containing and alkali-containing wastewater is greatly reduced, and the method is economical and environment-friendly.

Description

Boron removal method for isomerized lactose liquid
Technical Field
The invention relates to the technical field of preparation methods of isomerized lactose, in particular to a boron removal method of isomerized lactose liquid.
Background
Isomerized lactose, called lactulose in the medical field, is prepared by taking lactose as a raw material through isomerization reaction. Since isomerized lactose can proliferate beneficial intestinal flora, it is called prebiotic, it has functions of improving intestinal environment and relieving constipation, and is listed in pharmacopoeia by over 100 countries in the world for treating constipation and hepatic encephalopathy. In the aspect of treating constipation, the medicine is good in effect, suitable for infants and good in safety.
The isomerization lactose has the sweetness of 50-60% of that of cane sugar with the same concentration, has low calorie, does not cause the rise of blood sugar, is not only suitable for healthy people, but also is a functional sweetener suitable for diabetics.
The preparation method of the isomerized lactose comprises a chemical method and a biological method, wherein the biological method is in a research stage due to low conversion rate, and industrial production mainly adopts the chemical method, wherein the boric acid method has high conversion rate of isomerized lactose which can reach over 75 percent, which is a main method of the current industrial production, but because a large amount of boric acid and alkali solution are added in the isomerization process, particularly, the boric acid is difficult to remove, the method becomes a key technology which needs to be broken through in the production of the isomerized lactose, and a large amount of work is carried out by a plurality of research institutions and enterprises around the recovery and the utilization of boron and boron. As for the boron removal method, in the prior art, resin is adopted for removing boron, a nanofiltration membrane is adopted for removing boron, and due to the fact that the adding amount of boron in the production process is large, any single boron removal method cannot enable the content of boron to reach the edible standard, or boric acid and alkali solution used in the production process cannot be recycled, so that the production cost is increased, and environmental protection is not allowed.
Disclosure of Invention
In order to achieve the above object, the present invention provides a method for removing boron from an isomerized lactose liquid.
The technical scheme is as follows:
a method for removing boron from isomerized lactose liquid comprises the following steps:
(1) preparation of a crude isomerized lactose liquid: adding boric acid into lactose solution with certain concentration, adjusting pH value to 10.0-12.0 with alkali solution, and reacting at high temperature to obtain crude isomerized lactose liquid with pH value of 9.0-11.0;
(2) recovering an alkali solution by an electrodialysis method: enabling the crude isomerized lactose solution obtained in the step (1) to pass through an electrodialytic anode chamber, obtaining isomerized lactose solution and boric acid in an anode chamber under the action of an electric field, and obtaining alkali solution in a cathode chamber, wherein the pH value of the anode chamber is 2.0-3.0, and the alkali solution obtained in the cathode chamber can be reused for preparing the crude isomerized lactose solution in the step (1);
the principle of preparing isomerized lactose by the boric acid method is that boric acid is added into a lactose solution, the pH value is adjusted to be alkaline by alkali, lactose reacts under the alkaline condition to generate isomerized lactose, the generated isomerized lactose and borate form a complex of borate and isomerized lactose, the reaction balance is moved to the direction of generating isomerized lactose, the conversion rate of isomerized lactose is improved, and the generation of byproducts is reduced. After the reaction is completed, if the boric acid is directly removed by the nanofiltration membrane method, the pH value of the solution needs to be adjusted to about 3.0 by hydrochloric acid, so that the borate and the isomerized lactose complex are decomposed to obtain isomerized lactose, and the borate is converted into the boric acid under the acidic condition.
H obtained by anode ionization of water when recovering alkali solution by electrodialysis method+The method has the advantages that the method plays a role of acid, so that the borate and the isomerized lactose complex can be decomposed to obtain isomerized lactose without adding hydrochloric acid, the borate is converted into boric acid under an acidic condition, and the feeding requirement of a nanofiltration membrane for removing boron is met, which is not expected in the prior art. Meanwhile, hydrochloric acid is not required to be added additionally, and new impurity Cl is avoided-Due to Cl-The corrosion effect on common stainless steel greatly increases the manufacturing cost of equipment, thereby reducing the equipment investment, which is not expected in the prior art.
(3) Removing boron by using a nanofiltration membrane: removing boric acid from the anolyte obtained in the step (2) by adopting a nanofiltration membrane to obtain trapped fluid and permeate, wherein the trapped fluid mainly contains isomerized lactose and a small amount of unremoved boric acid, the permeate is boric acid, and the boric acid can be reused for preparing the crude isomerized lactose liquid in the step (1); the boron content of the nanofiltration membrane feed (in the invention, the boron content refers to the boron element content) is 2200-5000ppm, and the boron content of the membrane retention solution is 50-200 ppm.
(4) Boron removal by the boron removal resin: deeply removing boron from the trapped fluid in the step (3) through boron removing resin, so that the boron content in the product is controlled to be below 25 ppm. Because the solid content in the trapped fluid is low, boron removal is carried out after evaporation concentration, the solid concentration of the boron removal resin feeding is 30-55%, the boron content is 100-400ppm, the boron content of the boron removal resin discharging material is controlled below 5ppm, and the boron content in the final product is controlled below 25 ppm.
In the step (1), the concentration of the lactose solution is 20-50%, the addition amount of boric acid is 1:0.5-1:1 according to the molar ratio of lactose to boric acid, the reaction temperature is 65-90 ℃, and the reaction time is 1-4 h.
The alkali solution in the step (1) is sodium hydroxide or potassium hydroxide.
The electrodialysis device in the step (2) consists of an anode, a cathode and a cation exchange membrane, wherein catholyte is an alkaline solution, and the alkaline solution is sodium hydroxide or potassium hydroxide.
And (3) the solid concentration of the crude isomerized lactose liquid entering the electrodialytic anode chamber in the step (2) is 10-20%.
The molecular weight cut-off of the nanofiltration membrane in the step (3) is 150-250Da, the separation temperature is 15-40 ℃, and the separation pressure is 1.2-2.2 MPa.
Aiming at the problems in the prior art of isomerized lactose liquid, the invention provides a boron removal method of isomerized lactose liquid, and the technical scheme provided by the embodiment of the invention has the beneficial effects that:
1. the invention reduces the boron content in the isomerized lactose liquid to be within the edible safety standard;
2. the boric acid and the alkali solution added in the production process are recycled and reused, so that the production cost is reduced, the emission of boron-containing and alkali-containing wastewater is greatly reduced, and the method is economic and environment-friendly;
3. according to the method, an electrodialysis method is adopted to recover the alkali solution, boric acid is generated by roughly isomerizing borate in the lactose liquid while recovering the alkali solution, hydrochloric acid is not required to be added before nanofiltration, and the production consumption is saved;
4. the method adopts an electrodialysis method to recover the alkali solution, the boric acid is generated by roughly isomerizing the borate in the lactose liquid while recovering the alkali solution, hydrochloric acid is not required to be additionally added before nanofiltration, and new impurities Cl are avoided-The introduction of (2) reduces the manufacturing requirement of equipment and reduces the investment.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a schematic diagram of the recovery of an alkaline solution by electrodialysis.
Wherein the content of the first and second substances,
Figure DEST_PATH_IMAGE002
: an anode;
Figure DEST_PATH_IMAGE004
: a cathode; c: a cation exchange membrane.
Detailed Description
Example 1
Preparing lactose with the mass concentration of 40%, heating to dissolve, adding boric acid according to the molar mass ratio of 1:0.7 of the lactose to the boric acid, adjusting the pH value to 11.0 by using sodium hydroxide, reacting at the temperature of 75 ℃ for 1.5h, stopping the reaction to obtain crude isomerized lactose liquid, adjusting the mass concentration of the crude isomerized lactose liquid to 15% by using deionized water, entering an anode chamber of an electrodialysis device, adding 2% of sodium hydroxide into a cathode chamber, applying 5V direct current voltage for electrolysis for 2h, reducing the pH value of an anode to 2.5 to obtain isomerized lactose liquid and boric acid, obtaining 18.5% of sodium hydroxide at the cathode, and using the sodium hydroxide for the next batch of isomerized lactose production. Removing boron from the anolyte obtained in the electrodialytic anode chamber by adopting a nanofiltration membrane with the molecular weight cutoff of 150-250Da, controlling the temperature of materials at 20-40 ℃ and the pressure at 1.8MPa in the circulating process, removing boron by nanofiltration to obtain a trapped liquid and a permeate liquid, wherein the trapped liquid is an isomerized lactose liquid, the boron content is reduced to 160ppm from 3820ppm of the fed material, and the permeate liquid is a boric acid solution which is used for the next batch of isomerized lactose production. And then evaporating and concentrating the trapped fluid until the concentration of the solid is 45%, at the moment, the boron content is 320ppm, then removing boron by adopting resin, wherein the boron content of the discharged material of the boron-removed resin is 3ppm, and evaporating and concentrating to obtain an isomerized lactose product, wherein the boron content is 18 ppm.
Example 2
Preparing lactose with the mass concentration of 50%, heating to dissolve, adding boric acid according to the molar mass ratio of 1:1 of the lactose to the boric acid, adjusting the pH value to 12.0 by using sodium hydroxide, reacting at 90 ℃ for 2.5 hours, stopping the reaction to obtain a crude isomerized lactose liquid, adjusting the mass concentration of the crude isomerized lactose liquid to 20% by using deionized water, entering an anode chamber of an electrodialysis device, entering a cathode chamber, applying 6V direct current voltage for electrolysis for 1.5 hours, reducing the pH value of the anode to 2.2 to obtain isomerized lactose liquid and boric acid, obtaining the concentration of sodium hydroxide at the cathode of the electrodialysis device to be 20.3%, and using the sodium hydroxide for the next batch of isomerized lactose production. Removing boron from the anolyte obtained in the electrodialytic anode chamber by adopting a nanofiltration membrane with the molecular weight cutoff of 150-250Da, controlling the temperature of materials at 20-40 ℃ and the pressure at 2.2MPa in the circulating process, removing boron by nanofiltration to obtain a trapped liquid and a permeate liquid, wherein the trapped liquid is an isomerized lactose liquid, the boron content is reduced to 185ppm from 4910ppm of a feed, and the permeate liquid is a boric acid solution which is used for the next batch of isomerized lactose production. And then evaporating and concentrating the trapped fluid until the concentration of the solid is 55 percent, at the moment, the boron content is 388ppm, then removing boron by adopting resin, wherein the boron content of the discharged boron of the boron-removed resin is 4.6ppm, and evaporating and concentrating to obtain an isomerized lactose product, wherein the boron content is 23 ppm.
Example 3
Preparing lactose with the mass concentration of 20%, heating to dissolve, adding boric acid according to the molar mass ratio of 1:0.5 of lactose to boric acid, adjusting the pH value to 10.0 by using sodium hydroxide, reacting at 65 ℃ for 3.5 hours, stopping the reaction to obtain crude isomerized lactose liquid, adjusting the mass concentration of the crude isomerized lactose liquid to 10% by using deionized water, entering an anode chamber of an electrodialysis device, entering a cathode chamber, wherein the sodium hydroxide concentration is 2%, applying 4V direct current voltage for electrolysis for 3 hours, reducing the anode pH value to 2.7 to obtain isomerized lactose liquid and boric acid, obtaining the sodium hydroxide concentration at a cathode of 17.3%, and using the sodium hydroxide for the next batch of isomerized lactose production. Removing boron from the anolyte obtained in the electrodialytic anode chamber by adopting a nanofiltration membrane with the molecular weight cutoff of 150-250Da, controlling the temperature of materials at 20-40 ℃ and the pressure at 1.3MPa in the circulating process, removing boron by nanofiltration to obtain a cutoff liquid and a permeate liquid, wherein the cutoff liquid is an isomerized lactose liquid, the boron content is reduced to 65ppm from the feeding of 2340ppm, and the permeate liquid is a boric acid solution which is used for the next batch of isomerized lactose production. And then evaporating and concentrating the trapped fluid until the concentration of the solid is 30%, at the moment, the boron content is 145ppm, then removing boron by adopting resin, wherein the boron content of the discharged material of the boron-removed resin is 1ppm, and evaporating and concentrating to obtain an isomerized lactose product, wherein the boron content is 11 ppm.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A boron removal method for isomerized lactose liquid is characterized by comprising the following steps:
(1) preparation of a crude isomerized lactose liquid: adding boric acid into a lactose solution with a certain concentration, adjusting the pH value to 10.0-12.0 by adopting an alkali solution, and then reacting at a high temperature to obtain a crude isomerized lactose liquid;
(2) recovering an alkali solution by an electrodialysis method: enabling the crude isomerized lactose solution obtained in the step (1) to pass through an electrodialytic anode chamber, obtaining isomerized lactose solution and boric acid in an anode chamber under the action of an electric field, and obtaining alkali solution in a cathode chamber, wherein the pH value of the anode chamber is 2.0-3.0, and the alkali solution obtained in the cathode chamber can be reused for preparing the crude isomerized lactose solution in the step (1);
(3) removing boron by using a nanofiltration membrane: removing boric acid from the anolyte obtained in the step (2) by adopting a nanofiltration membrane to obtain trapped fluid and permeate, wherein the trapped fluid mainly contains isomerized lactose and a small amount of unremoved boric acid, the permeate is boric acid, and the boric acid can be reused for preparing the crude isomerized lactose liquid in the step (1);
(4) boron removal by the boron removal resin: deeply removing boron from the trapped fluid in the step (3) through boron removing resin, so that the boron content in the product is controlled to be below 25 ppm.
2. The method for removing boron from the isomerized lactose liquid in claim 1, wherein the concentration of the lactose solution in the step (1) is 20-50%, the addition amount of the boric acid is 1:0.5-1:1 according to the molar ratio of lactose to boric acid, the reaction temperature is 65-90 ℃, and the reaction time is 1-4 h.
3. The method for removing boron from an isomerized lactose liquid as claimed in claim 1, wherein the alkali solution in step (1) is sodium hydroxide or potassium hydroxide.
4. The method for removing boron from an isomerized lactose liquid as claimed in claim 1, wherein the device for electrodialysis in step (2) consists of an anode, a cathode and a cation exchange membrane, the catholyte is an alkaline solution, and the alkaline solution is sodium hydroxide or potassium hydroxide.
5. The method for removing boron from an isomerized lactose liquid as claimed in claim 1, wherein the solid concentration of the crude isomerized lactose liquid entering the electrodialytic anode chamber in step (2) is 10-20%.
6. The method for removing boron from the isomerized lactose liquid as claimed in claim 1, wherein the molecular weight cut-off of the nanofiltration membrane in the step (3) is 150-250Da, the separation temperature is 15-40 ℃, and the separation pressure is 1.2-2.2 MPa.
CN202111527595.2A 2021-12-15 2021-12-15 Boron removal method for isomerized lactose liquid Pending CN114028949A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111527595.2A CN114028949A (en) 2021-12-15 2021-12-15 Boron removal method for isomerized lactose liquid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111527595.2A CN114028949A (en) 2021-12-15 2021-12-15 Boron removal method for isomerized lactose liquid

Publications (1)

Publication Number Publication Date
CN114028949A true CN114028949A (en) 2022-02-11

Family

ID=80146988

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111527595.2A Pending CN114028949A (en) 2021-12-15 2021-12-15 Boron removal method for isomerized lactose liquid

Country Status (1)

Country Link
CN (1) CN114028949A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114682244A (en) * 2022-06-01 2022-07-01 浙江晟格生物科技有限公司 Recovery method of lactose isomerization composite catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0692542A1 (en) * 1994-07-11 1996-01-17 Duphar International Research B.V Process for the separation of lactulose
CN103864858A (en) * 2014-03-11 2014-06-18 江南大学 Preparation method of lactulose

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0692542A1 (en) * 1994-07-11 1996-01-17 Duphar International Research B.V Process for the separation of lactulose
CN103864858A (en) * 2014-03-11 2014-06-18 江南大学 Preparation method of lactulose

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114682244A (en) * 2022-06-01 2022-07-01 浙江晟格生物科技有限公司 Recovery method of lactose isomerization composite catalyst
CN114682244B (en) * 2022-06-01 2022-08-23 浙江晟格生物科技有限公司 Recovery method of lactose isomerization composite catalyst

Similar Documents

Publication Publication Date Title
EP2118294B1 (en) Method of producing xylitol using hydrolysate containing xylose and arabinose prepared from byproduct of tropical fruit biomass
EP2495329B1 (en) Process for economically manufacturing xylose from hydrolysate using electrodialysis and direct recovery method
CN109097408B (en) Preparation method of nylon 56 salt
US20180327796A1 (en) Method of producing high purity d-psicose
EP1080776A3 (en) Electrodialysis water splitting process
CN109516479B (en) Preparation method of battery-grade lithium hydroxide
CN108468065B (en) Sodium chlorate and chlor-alkali combined denitration process
CN109592699B (en) Preparation method of battery-grade lithium hydroxide
CN114028949A (en) Boron removal method for isomerized lactose liquid
CN111548323B (en) Recovery method of aminothiazoly loximate
CN110776543A (en) Method for recovering adenosine primary mother liquor
CN111574358A (en) Preparation process of potassium diformate
CN113443639B (en) Preparation process of electronic grade potassium hydroxide
US4874700A (en) Process for the production of L-malic acid
EP2749649B1 (en) Method for separating and purifying 1,4-diaminobutane from fermented solution
EP2598468A1 (en) Method for recovering an auxiliary used in a fermentation procedure for producing a product
EP3119792B1 (en) Process for isolating fermentable sugars from the acid hydrolyzate of a material containing cellulose, hemicellulose and lignin
CN112209412B (en) Method for extracting lithium and battery-grade lithium hydroxide monohydrate
CN111573762B (en) Method for treating deplating waste liquid of printed circuit board
CN106589006A (en) Boracic acid recovery and reutilization method in lactulose preparation
CN103508848B (en) Method for producing mannitol and sorbitol through waste fructooligosaccharide liquid
CN108585006B (en) Method for active dissolution and raw material preparation in aluminum ash treatment process
CN214299947U (en) 1, 5-pentanediamine extraction system
CN114315599A (en) Extraction method of 1, 5-pentanediamine and obtained 1, 5-pentanediamine product
US3130082A (en) Sugar recovery process and products

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination