CN117431348A - High-purity environment-friendly lactulose concentrated solution and preparation method thereof - Google Patents
High-purity environment-friendly lactulose concentrated solution and preparation method thereof Download PDFInfo
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- CN117431348A CN117431348A CN202311517163.2A CN202311517163A CN117431348A CN 117431348 A CN117431348 A CN 117431348A CN 202311517163 A CN202311517163 A CN 202311517163A CN 117431348 A CN117431348 A CN 117431348A
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- JCQLYHFGKNRPGE-FCVZTGTOSA-N lactulose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 JCQLYHFGKNRPGE-FCVZTGTOSA-N 0.000 title claims abstract description 106
- 229960000511 lactulose Drugs 0.000 title claims abstract description 106
- PFCRQPBOOFTZGQ-UHFFFAOYSA-N lactulose keto form Natural products OCC(=O)C(O)C(C(O)CO)OC1OC(CO)C(O)C(O)C1O PFCRQPBOOFTZGQ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims abstract description 42
- 239000008101 lactose Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003463 adsorbent Substances 0.000 claims abstract description 30
- 230000000536 complexating effect Effects 0.000 claims abstract description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 17
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 238000001728 nano-filtration Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- 238000003756 stirring Methods 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000706 filtrate Substances 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 238000000967 suction filtration Methods 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000012047 saturated solution Substances 0.000 claims description 15
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- ZXBLVTLRLTWNRE-UHFFFAOYSA-N [3-(prop-2-enoylamino)phenoxy]boronic acid Chemical compound OB(O)Oc1cccc(NC(=O)C=C)c1 ZXBLVTLRLTWNRE-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004042 decolorization Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003517 fume Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 9
- 239000005018 casein Substances 0.000 abstract description 9
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 abstract description 9
- 235000021240 caseins Nutrition 0.000 abstract description 9
- 235000013351 cheese Nutrition 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000006317 isomerization reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 2
- 238000012674 dispersion polymerization Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- ULVXDHIJOKEBMW-UHFFFAOYSA-N [3-(prop-2-enoylamino)phenyl]boronic acid Chemical compound OB(O)C1=CC=CC(NC(=O)C=C)=C1 ULVXDHIJOKEBMW-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/005—Lactulose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
Abstract
The invention relates to the technical field of lactulose preparation methods, in particular to a high-purity environment-friendly lactulose concentrated solution and a preparation method thereof, wherein a self-made complexing adsorbent is prepared by adopting a dispersion polymerization method, and the self-made complexing adsorbent is added into the lactulose to adsorb produced lactulose in the lactose isomerization process, so that the conversion rate of the lactulose is improved to a certain extent; secondly, pouring the self-made complexing adsorbent adsorbed with the lactulose into a hydrochloric acid solution for desorption, dissolving the lactulose into the hydrochloric acid solution, decolorizing, and then carrying out nanofiltration by a roll-type membrane ultrafiltration device to obtain a lactulose concentrated solution with higher purity, and rapidly removing calcium hydroxide in reaction components by adding carbon dioxide, thereby being beneficial to the recovery of the lactulose; finally, lactose byproducts generated in the cheese and casein production process are used as raw materials, so that the environment-friendly effect of saving resources and utilizing waste can be achieved.
Description
Technical Field
The invention relates to the technical field of lactulose preparation methods, in particular to a high-purity environment-friendly lactulose concentrated solution and a preparation method thereof.
Background
Lactulose is an organic matter, is a light yellow transparent viscous liquid, is disaccharide composed of galactose and fructose, does not exist in the natural world, generally appears as a syrup-like product, and is widely used in the fields of clinical medicine, health care products, food additives and the like. And the lactulose has various functional characteristics of low calorie, spleen strengthening, intestine moisturizing, li Gan brain strengthening and the like, and has wide application in food production and clinical application as a good flavoring agent. At present, chemical synthesis or biological fermentation methods are used for synthesizing lactulose, and the traditional biological fermentation methods have the defects of complicated operation process, long production period, and more waste materials, which are unfavorable for industrial production, because the chemical synthesis process is complicated, the conversion rate is lower, and the cost is high.
The existing commercial lactulose is mainly prepared by chemical isomerization of lactose in a high-temperature strong alkaline environment, the conversion rate of the lactulose can be effectively improved by adding the complexing agent, the lactulose which is converted is adsorbed into the complexing agent in the process of converting the lactose into the lactulose, and then the lactulose is desorbed into the solution from the complexing agent, so that the purity of the prepared lactulose can be improved on the basis of improving the conversion rate of the lactulose, and the adsorption capacity of the lactulose by the complexing agent is far greater than that of the lactose, so that the effect of improving the purity of the lactulose can be achieved by adsorbing the lactulose by the complexing agent.
In the industrial production process of cheese and casein, about 900 tens of thousands tons of byproduct lactose can be wasted every year worldwide, and if the lactose can be used as a raw material to prepare high-purity lactulose through processing, the cost in the preparation process of the lactulose can be saved to a certain extent. However, in the prior art, a method for preparing high-purity lactulose by using lactose byproducts generated in the production process of cheese and casein as raw materials is not described, so if a preparation method can be designed to prepare high-purity lactulose by using lactose byproducts generated in the production process of cheese and casein as raw materials, the raw material cost in the preparation process of lactulose can be reduced to a great extent.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects existing in the prior art, the invention provides a high-purity environment-friendly lactulose concentrated solution and a preparation method thereof, aiming at preparing high-purity lactulose by taking lactose with lower cost as a raw material.
Technical proposal
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a method for preparing a high-purity environment-friendly lactulose concentrated solution, which comprises the following steps:
step1, dropwise adding a calcium hydroxide saturated solution into a lactose solution until the pH value is 10-13, heating to 60-70 ℃, and reacting for 20-30min under the stirring condition, wherein the obtained mixture is taken as a component to be reacted;
step2, adding 3-5% of self-made complexing adsorbent components by weight into the components to be reacted in Step1, continuously stirring at an original stirring speed for 50-60min under an original temperature condition, continuously dropwise adding a calcium hydroxide saturated solution in the stirring process, and maintaining the pH value of the components to be reacted to be 11-13, wherein the obtained components are marked as components to be purified;
step3, carrying out suction filtration on the components to be purified in Step2 to obtain initial filtrate and initial filter residues, pouring the initial filter residues into hydrochloric acid solution with the volume being 10 times of that of the initial filter residues, stirring for 15-30min, and carrying out suction filtration again, wherein the obtained filtrate is taken as a first component of lactulose;
step4, introducing carbon dioxide into the initial filtrate in Step3 at a flow rate of 10m/s, performing suction filtration until the initial filtrate is neutral, marking the obtained filtrate as a lactulose second component, mixing the obtained filtrate with the lactulose first component in Step3, and marking the obtained filtrate as a lactulose component after decolorization treatment;
step5, dropwise adding sodium hydroxide solution into the lactulose component to adjust the pH value to 7, pouring the lactulose component into a roll-type membrane ultrafiltration device, and carrying out interception nanofiltration by using a nanofiltration membrane with the interception molecular weight of 400u under the conditions of 0.45MPa and 25 ℃, wherein the obtained interception liquid is the high-purity environment-friendly lactulose concentrated solution.
Further, the concentration of the lactose solution in Step1 is 40%, lactose in the lactose solution is a lactose byproduct generated in the cheese and casein production process, and the stirring speed in Step1 is 100-150r/min.
Further, the preparation method of the self-made complexing adsorbent component comprises the following steps:
step1, weighing 0.2g of polyvinylpyrrolidone, dissolving in 10mL of absolute methanol, mixing and stirring uniformly, and marking as a dispersing agent component;
step2, weighing 8-10 mol of 3-acrylamidophenylboric acid and 20-25mol of ethylene glycol dimethacrylate, pouring the mixture into a flask filled with 5mL of absolute methanol, adding 20mL of acetonitrile for shaking mixing, and then adding the dispersant component and 40mg of azodiisobutyronitrile in the step1, wherein the obtained mixture is recorded as a mixed component;
step3, placing the mixed components in the step2 into an ultrasonic generator, introducing nitrogen for 5min after ultrasonic degassing for 15min, sealing, placing into a water bath shaking table at 55-60 ℃ for oscillation polymerization, cooling to normal temperature, and filtering to obtain a granular polymer;
and 4, placing the granular polymer in the step3 in a Soxhlet extractor, adding a methanol-acetic acid mixed solvent, extracting for 12 hours at the temperature of 80 ℃, washing to be neutral by using absolute methanol, placing in a fume hood, volatilizing more residual methanol, and drying in a vacuum drying oven at 60 ℃ for 5-6 hours to obtain the self-made complexing adsorbent component.
Further, the stirring speed of the mixing and stirring in the step1 is 100-200r/min, and the stirring time is 2-3min.
Further, the rotational speed of the oscillation polymerization in the step3 is 150r/min, and the time is 24-26h.
Furthermore, the methanol-acetic acid mixed solvent in the step4 is prepared by mixing methanol and acetic acid according to an equal volume ratio.
Furthermore, the concentration of the hydrochloric acid solution in Step3 is 0.1mol/L, and the filter residue in Step3 is washed by deionized water for 3 times and dried, thus obtaining the recyclable self-made complexing adsorbent component.
Further, the specific method for decoloring Step4 is as follows: adding 5-8% of active carbon into the component of Step3 subjected to suction filtration to remove filter residues, stirring at 50 ℃ and stirring speed of 80-100r/min for 28-30min, and performing suction filtration again to remove filter residues.
Further, the concentration of the sodium hydroxide solution in Step5 is 1mol/L.
The preparation raw materials of the high-purity environment-friendly lactulose concentrated solution comprise: lactose solution with concentration of 40%, calcium hydroxide saturated solution, hydrochloric acid solution with concentration of 0.1mol/L, sodium hydroxide solution with concentration of 1mol/L, carbon dioxide, polyvinylpyrrolidone solution, 3-acrylamidophenylboric acid, ethylene glycol dimethacrylate, acetonitrile and azodiisobutyronitrile.
Advantageous effects
The invention provides a high-purity environment-friendly lactulose concentrated solution and a preparation method thereof, and compared with the prior art, the invention has the following beneficial effects:
according to the invention, acetonitrile is used as a continuous phase, 3-acrylamidophenylboronic acid is used as a functional monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, polyvinylpyrrolidone is used as a dispersing agent, a self-made complexing adsorbent is prepared by adopting a dispersion polymerization method, and the self-made complexing adsorbent has a large adsorption capacity on lactulose, so that the produced lactulose can be adsorbed in the lactose isomerization process, and the conversion rate of the lactulose is improved to a certain extent; secondly, pouring the self-made complexing adsorbent adsorbed with the lactulose into a hydrochloric acid solution for desorption, dissolving the lactulose into the hydrochloric acid solution, and purifying the lactulose solution through nanofiltration of a roll-type membrane ultrafiltration device after decolorization, so that a lactulose concentrated solution with higher purity is prepared, and calcium hydroxide in reaction components can be rapidly removed through addition of carbon dioxide, thereby being beneficial to recovery of the lactulose; finally, lactose byproducts generated in the cheese and casein production process are used as raw materials, so that the environment-friendly effect of saving resources and utilizing waste can be achieved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further described below with reference to examples.
Example 1
The preparation method of the high-purity environment-friendly lactulose concentrated solution comprises the following steps of:
step1, dropwise adding a calcium hydroxide saturated solution into a lactose solution until the pH value is 10, heating to 60 ℃, and reacting for 20min under the stirring condition that the stirring speed is 100r/min, wherein the obtained mixture is marked as a component to be reacted;
wherein the concentration of lactose solution is 40%, and lactose in lactose solution is lactose byproduct generated in cheese and casein production process.
Step2, adding a self-made complexing adsorbent component accounting for 3% of the weight of the self-made complexing adsorbent component into the component to be reacted in Step1, continuously stirring for 50min at an original stirring speed under an original temperature condition, continuously dropwise adding a calcium hydroxide saturated solution in the stirring process, maintaining the pH value of the component to be reacted to be 11, and marking the obtained component as a component to be purified;
the preparation method of the self-made complexing adsorbent component comprises the following steps:
step1, weighing 0.2g of polyvinylpyrrolidone, dissolving in 10mL of absolute methanol, uniformly mixing and stirring, and marking the mixture as a dispersing agent component, wherein the stirring speed of mixing and stirring is 100r/min, and the stirring time is 2min;
step2, weighing 8mol of 3-acrylamidophenylboric acid and 20mol of ethylene glycol dimethacrylate, pouring the mixture into a flask filled with 5mL of absolute methanol, adding 20mL of acetonitrile for shaking mixing, and adding the dispersant component and 40mg of azodiisobutyronitrile in the step1, wherein the obtained mixture is recorded as a mixed component;
step3, placing the mixed components in the step2 in an ultrasonic generator, introducing nitrogen for 5min after ultrasonic degassing for 15min, sealing, placing in a water bath shaking table at 55 ℃ for oscillation polymerization, wherein the rotation speed of the oscillation polymerization is 150r/min, the time is 24h, then cooling to normal temperature, and obtaining a granular polymer after suction filtration;
and 4, placing the granular polymer in the step3 in a Soxhlet extractor, adding a methanol-acetic acid mixed solvent prepared by mixing methanol and acetic acid according to an equal volume ratio, extracting for 12 hours at the temperature of 80 ℃, washing to be neutral by using absolute methanol, placing in a fume hood, volatilizing more than residual methanol, and drying in a vacuum drying oven at 60 ℃ for 5 hours to obtain the self-made complexing adsorbent component.
Step3, carrying out suction filtration on the components to be purified in Step2 to obtain initial filtrate and initial filter residues, pouring the initial filter residues into hydrochloric acid solution with 10 times of the volume of the initial filter residues and the concentration of 0.1mol/L, stirring for 15min, and carrying out suction filtration again to obtain filtrate which is taken as a first component of lactulose; and washing the filter residue subjected to suction filtration with deionized water for 3 times and drying to obtain the recyclable self-made complexing adsorbent component.
Step4, introducing carbon dioxide into the initial filtrate in Step3 at a flow rate of 10m/s, performing suction filtration until the initial filtrate is neutral, marking the obtained filtrate as a lactulose second component, mixing the obtained filtrate with the lactulose first component in Step3, and marking the obtained filtrate as a lactulose component after decolorization treatment;
the specific method for decoloring comprises the following steps: adding 5% of active carbon into the component of Step3 subjected to suction filtration to remove filter residues, stirring at a stirring speed of 80r/min for 28min at a temperature of 50 ℃, and performing suction filtration again to remove filter residues.
Step5, dropwise adding a sodium hydroxide solution with the concentration of 1mol/L into the lactulose component to adjust the pH value to 7, then pouring the lactulose component into a roll-type membrane ultrafiltration device, and carrying out interception nanofiltration by using a nanofiltration membrane with the interception molecular weight of 400u under the conditions of 0.45MPa and 25 ℃, wherein the obtained interception liquid is the high-purity environment-friendly lactulose concentrated solution.
The preparation raw materials of the high-purity environment-friendly lactulose concentrated solution comprise: lactose solution with concentration of 40%, calcium hydroxide saturated solution, hydrochloric acid solution with concentration of 0.1mol/L, sodium hydroxide solution with concentration of 1mol/L, carbon dioxide, polyvinylpyrrolidone solution, 3-acrylamidophenylboric acid, ethylene glycol dimethacrylate, acetonitrile and azodiisobutyronitrile.
Example 2
The preparation method of the high-purity environment-friendly lactulose concentrated solution comprises the following steps of:
step1, dropwise adding a calcium hydroxide saturated solution into a lactose solution until the pH value is 13, heating to 70 ℃, and reacting for 30min under the stirring condition that the stirring speed is 150r/min, wherein the obtained mixture is marked as a component to be reacted;
wherein the concentration of lactose solution is 40%, and lactose in lactose solution is lactose byproduct generated in cheese and casein production process.
Step2, adding a self-made complexing adsorbent component accounting for 5% of the weight of the self-made complexing adsorbent component into the component to be reacted in Step1, continuously stirring at an original stirring speed for 60min under an original temperature condition, continuously dropwise adding a calcium hydroxide saturated solution in the stirring process, maintaining the pH value of the component to be reacted to be 13, and marking the obtained component as a component to be purified;
the preparation method of the self-made complexing adsorbent component comprises the following steps:
step1, weighing 0.2g of polyvinylpyrrolidone, dissolving in 10mL of absolute methanol, uniformly mixing and stirring, and marking the mixture as a dispersing agent component, wherein the stirring speed of mixing and stirring is 200r/min, and the stirring time is 3min;
step2, weighing 10 mol of 3-acrylamidophenylboric acid and 25mol of ethylene glycol dimethacrylate, pouring the mixture into a flask filled with 5mL of absolute methanol, adding 20mL of acetonitrile for shaking mixing, and adding the dispersant component and 40mg of azodiisobutyronitrile in the step1, wherein the obtained mixture is recorded as a mixed component;
step3, placing the mixed components in the step2 in an ultrasonic generator, introducing nitrogen for 5min after ultrasonic degassing for 15min, sealing, placing in a water bath shaking table at 60 ℃ for oscillation polymerization, wherein the rotation speed of the oscillation polymerization is 150r/min, the time is 26h, then cooling to normal temperature, and obtaining a granular polymer after suction filtration;
and 4, placing the granular polymer in the step3 in a Soxhlet extractor, adding a methanol-acetic acid mixed solvent prepared by mixing methanol and acetic acid according to an equal volume ratio, extracting for 12 hours at the temperature of 80 ℃, washing to be neutral by using absolute methanol, placing in a fume hood, volatilizing more than residual methanol, and drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain the self-made complexing adsorbent component.
Step3, carrying out suction filtration on the components to be purified in Step2 to obtain initial filtrate and initial filter residues, pouring the initial filter residues into a hydrochloric acid solution with 10 times of the volume of the initial filter residues and the concentration of 0.1mol/L, stirring for 30min, and carrying out suction filtration again to obtain filtrate which is taken as a first component of lactulose; and washing the filter residue subjected to suction filtration with deionized water for 3 times and drying to obtain the recyclable self-made complexing adsorbent component.
Step4, introducing carbon dioxide into the initial filtrate in Step3 at a flow rate of 10m/s, performing suction filtration until the initial filtrate is neutral, marking the obtained filtrate as a lactulose second component, mixing the obtained filtrate with the lactulose first component in Step3, and marking the obtained filtrate as a lactulose component after decolorization treatment;
the specific method for decoloring comprises the following steps: adding 8% of activated carbon into the component of Step3 subjected to suction filtration to remove filter residues, stirring at a stirring speed of 100r/min for 30min at a temperature of 50 ℃, and performing suction filtration again to remove filter residues.
Step5, dropwise adding a sodium hydroxide solution with the concentration of 1mol/L into the lactulose component to adjust the pH value to 7, then pouring the lactulose component into a roll-type membrane ultrafiltration device, and carrying out interception nanofiltration by using a nanofiltration membrane with the interception molecular weight of 400u under the conditions of 0.45MPa and 25 ℃, wherein the obtained interception liquid is the high-purity environment-friendly lactulose concentrated solution.
The preparation raw materials of the high-purity environment-friendly lactulose concentrated solution comprise: lactose solution with concentration of 40%, calcium hydroxide saturated solution, hydrochloric acid solution with concentration of 0.1mol/L, sodium hydroxide solution with concentration of 1mol/L, carbon dioxide, polyvinylpyrrolidone solution, 3-acrylamidophenylboric acid, ethylene glycol dimethacrylate, acetonitrile and azodiisobutyronitrile.
Example 3
The preparation method of the high-purity environment-friendly lactulose concentrated solution comprises the following steps of:
step1, dropwise adding a calcium hydroxide saturated solution into a lactose solution until the pH value is 12, heating to 65 ℃, and reacting for 25min under the stirring condition that the stirring speed is 150r/min, wherein the obtained mixture is marked as a component to be reacted;
wherein the concentration of lactose solution is 40%, and lactose in lactose solution is lactose byproduct generated in cheese and casein production process.
Step2, adding a self-made complexing adsorbent component accounting for 4% of the weight of the self-made complexing adsorbent component into the component to be reacted in Step1, continuously stirring for 55min at the original stirring speed under the original temperature condition, continuously dropwise adding a calcium hydroxide saturated solution in the stirring process, maintaining the pH value of the component to be reacted to be 12, and recording the obtained component as the component to be purified;
the preparation method of the self-made complexing adsorbent component comprises the following steps:
step1, weighing 0.2g of polyvinylpyrrolidone, dissolving in 10mL of absolute methanol, uniformly mixing and stirring, and marking the mixture as a dispersing agent component, wherein the stirring speed of mixing and stirring is 100r/min, and the stirring time is 3min;
step2, weighing 9mol of 3-acrylamidophenylboric acid and 22mol of ethylene glycol dimethacrylate, pouring the mixture into a flask filled with 5mL of absolute methanol, adding 20mL of acetonitrile for shaking mixing, and adding the dispersant component and 40mg of azodiisobutyronitrile in the step1, wherein the obtained mixture is recorded as a mixed component;
step3, placing the mixed components in the step2 in an ultrasonic generator, introducing nitrogen for 5min after ultrasonic degassing for 15min, sealing, placing in a water bath shaking table at 58 ℃ for oscillation polymerization, wherein the rotation speed of the oscillation polymerization is 150r/min, the time is 25h, then cooling to normal temperature, and obtaining a granular polymer after suction filtration;
and 4, placing the granular polymer in the step3 in a Soxhlet extractor, adding a methanol-acetic acid mixed solvent prepared by mixing methanol and acetic acid according to an equal volume ratio, extracting for 12 hours at the temperature of 80 ℃, washing to be neutral by using absolute methanol, placing in a fume hood, volatilizing more than residual methanol, and drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain the self-made complexing adsorbent component.
Step3, carrying out suction filtration on the components to be purified in Step2 to obtain initial filtrate and initial filter residues, pouring the initial filter residues into hydrochloric acid solution with 10 times of the volume of the initial filter residues and the concentration of 0.1mol/L, stirring for 22min, and carrying out suction filtration again to obtain filtrate which is taken as a first component of lactulose; and washing the filter residue subjected to suction filtration with deionized water for 3 times and drying to obtain the recyclable self-made complexing adsorbent component.
Step4, introducing carbon dioxide into the initial filtrate in Step3 at a flow rate of 10m/s, performing suction filtration until the initial filtrate is neutral, marking the obtained filtrate as a lactulose second component, mixing the obtained filtrate with the lactulose first component in Step3, and marking the obtained filtrate as a lactulose component after decolorization treatment;
the specific method for decoloring comprises the following steps: adding 7% of active carbon into the component of Step3 subjected to suction filtration to remove filter residues, stirring at a stirring speed of 90r/min for 29min at a temperature of 50 ℃, and performing suction filtration again to remove filter residues.
Step5, dropwise adding a sodium hydroxide solution with the concentration of 1mol/L into the lactulose component to adjust the pH value to 7, then pouring the lactulose component into a roll-type membrane ultrafiltration device, and carrying out interception nanofiltration by using a nanofiltration membrane with the interception molecular weight of 400u under the conditions of 0.45MPa and 25 ℃, wherein the obtained interception liquid is the high-purity environment-friendly lactulose concentrated solution.
The preparation raw materials of the high-purity environment-friendly lactulose concentrated solution comprise: lactose solution with concentration of 40%, calcium hydroxide saturated solution, hydrochloric acid solution with concentration of 0.1mol/L, sodium hydroxide solution with concentration of 1mol/L, carbon dioxide, polyvinylpyrrolidone solution, 3-acrylamidophenylboric acid, ethylene glycol dimethacrylate, acetonitrile and azodiisobutyronitrile.
Comparative example
The preparation method of the high-purity environment-friendly lactulose concentrated solution provided by the comparative example is approximately the same as that of the example 1, and the main difference is that: comparative example 1 the homemade complexing adsorbent of example 1 was replaced with boric acid and the steps of Step3 and Step4 of example 1 were replaced with: introducing carbon dioxide into the component to be purified at a flow rate of 10m/s, carrying out suction filtration to remove calcium carbonate precipitate after the initial filtrate is neutral, continuously introducing carbon dioxide until the pH value in the system is 3, separating out boric acid precipitate, carrying out suction filtration to remove filter residues, and decolorizing to obtain the lactulose component.
Performance testing
The high purity, environmentally friendly concentrated lactulose solutions prepared in examples 1-3 were labeled as example 1, example 2, example 3 and comparative example, respectively, and then the lactulose purity in examples 1-3 and comparative example was examined by high performance liquid chromatography, and the conversion rate of lactose into lactulose was examined, and the obtained data were recorded in the following table:
as shown by the data in the table above, the purity of the high-purity environment-friendly lactulose concentrated solution prepared in the examples 1-3 is higher than 94%, and the conversion rate of lactose to lactulose is higher than 85%, so that the preparation method provided by the invention can prepare the lactulose concentrated solution with higher purity on the basis of improving the conversion rate of lactose to lactulose, and the preparation method provided by the invention has excellent market application value.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the high-purity environment-friendly lactulose concentrated solution is characterized by comprising the following steps of:
step1, dropwise adding a calcium hydroxide saturated solution into a lactose solution until the pH value is 10-13, heating to 60-70 ℃, and reacting for 20-30min under the stirring condition, wherein the obtained mixture is taken as a component to be reacted;
step2, adding 3-5% of self-made complexing adsorbent components by weight into the components to be reacted in Step1, continuously stirring at an original stirring speed for 50-60min under an original temperature condition, continuously dropwise adding a calcium hydroxide saturated solution in the stirring process, and maintaining the pH value of the components to be reacted to be 11-13, wherein the obtained components are marked as components to be purified;
step3, carrying out suction filtration on the components to be purified in Step2 to obtain initial filtrate and initial filter residues, pouring the initial filter residues into hydrochloric acid solution with the volume being 10 times of that of the initial filter residues, stirring for 15-30min, and carrying out suction filtration again, wherein the obtained filtrate is taken as a first component of lactulose;
step4, introducing carbon dioxide into the initial filtrate in Step3 at a flow rate of 10m/s, performing suction filtration until the initial filtrate is neutral, marking the obtained filtrate as a lactulose second component, mixing the obtained filtrate with the lactulose first component in Step3, and marking the obtained filtrate as a lactulose component after decolorization treatment;
step5, dropwise adding sodium hydroxide solution into the lactulose component to adjust the pH value to 7, pouring the lactulose component into a roll-type membrane ultrafiltration device, and carrying out interception nanofiltration by using a nanofiltration membrane with the interception molecular weight of 400u under the conditions of 0.45MPa and 25 ℃, wherein the obtained interception liquid is the high-purity environment-friendly lactulose concentrated solution.
2. The method for preparing the high-purity environmental-friendly lactulose concentrated solution according to claim 1, wherein the concentration of the lactose solution in Step1 is 40%, and the stirring speed in Step1 is 100-150r/min.
3. The method for preparing the high-purity environment-friendly lactulose concentrated solution according to claim 1, wherein the method for preparing the self-made complexing adsorbent component comprises the following steps:
step1, weighing 0.2g of polyvinylpyrrolidone, dissolving in 10mL of absolute methanol, mixing and stirring uniformly, and marking as a dispersing agent component;
step2, weighing 8-10 mol of 3-acrylamidophenylboric acid and 20-25mol of ethylene glycol dimethacrylate, pouring the mixture into a flask filled with 5mL of absolute methanol, adding 20mL of acetonitrile for shaking mixing, and then adding the dispersant component and 40mg of azodiisobutyronitrile in the step1, wherein the obtained mixture is recorded as a mixed component;
step3, placing the mixed components in the step2 into an ultrasonic generator, introducing nitrogen for 5min after ultrasonic degassing for 15min, sealing, placing into a water bath shaking table at 55-60 ℃ for oscillation polymerization, cooling to normal temperature, and filtering to obtain a granular polymer;
and 4, placing the granular polymer in the step3 in a Soxhlet extractor, adding a methanol-acetic acid mixed solvent, extracting for 12 hours at the temperature of 80 ℃, washing to be neutral by using absolute methanol, placing in a fume hood, volatilizing more residual methanol, and drying in a vacuum drying oven at 60 ℃ for 5-6 hours to obtain the self-made complexing adsorbent component.
4. The method for preparing high-purity environmental-friendly lactulose concentrated solution according to claim 3, wherein the stirring speed of the mixing and stirring in the step1 is 100-200r/min, and the stirring time is 2-3min.
5. The method for preparing high-purity and environment-friendly lactulose concentrated solution according to claim 3, wherein the rotational speed of the shaking polymerization in the step3 is 150r/min, and the time is 24-26h.
6. The method for preparing high-purity environmental-friendly lactulose concentrated solution according to claim 3, wherein the methanol-acetic acid mixed solvent in the step4 is prepared by mixing methanol and acetic acid according to an equal volume ratio.
7. The method for preparing the high-purity environment-friendly lactulose concentrated solution according to claim 1, wherein the concentration of the hydrochloric acid solution in Step3 is 0.1mol/L, and the filter residue in Step3 is washed with deionized water for 3 times and dried to obtain the recyclable self-made complex adsorbent component.
8. The method for preparing the high-purity environment-friendly lactulose concentrated solution according to claim 1, wherein the specific method for decoloring Step4 is as follows: adding 5-8% of active carbon into the component of Step3 subjected to suction filtration to remove filter residues, stirring at 50 ℃ and stirring speed of 80-100r/min for 28-30min, and performing suction filtration again to remove filter residues.
9. The method for preparing the high-purity environmental-friendly lactulose concentrated solution according to claim 1, wherein the concentration of the sodium hydroxide solution in Step5 is 1mol/L.
10. A high-purity environmental-friendly lactulose concentrated solution prepared by the preparation method of the high-purity environmental-friendly lactulose concentrated solution as claimed in any one of claims 1 to 9, characterized in that the raw materials for preparing the high-purity environmental-friendly lactulose concentrated solution comprise: lactose solution with concentration of 40%, calcium hydroxide saturated solution, hydrochloric acid solution with concentration of 0.1mol/L, sodium hydroxide solution with concentration of 1mol/L, carbon dioxide, polyvinylpyrrolidone solution, 3-acrylamidophenylboric acid, ethylene glycol dimethacrylate, acetonitrile and azodiisobutyronitrile.
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