CN116003485B - Preparation method of lactulose - Google Patents
Preparation method of lactulose Download PDFInfo
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- CN116003485B CN116003485B CN202310008537.1A CN202310008537A CN116003485B CN 116003485 B CN116003485 B CN 116003485B CN 202310008537 A CN202310008537 A CN 202310008537A CN 116003485 B CN116003485 B CN 116003485B
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- boron
- graphene oxide
- mannitol
- lactose
- tetrahydroxy
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- 229960000511 lactulose Drugs 0.000 title claims abstract description 68
- 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 66
- 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 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 212
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 140
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 140
- 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 92
- 239000008101 lactose Substances 0.000 claims abstract description 91
- -1 boron ions Chemical class 0.000 claims abstract description 77
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 40
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004327 boric acid Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 27
- 229930195725 Mannitol Natural products 0.000 claims abstract description 27
- 239000000594 mannitol Substances 0.000 claims abstract description 27
- 235000010355 mannitol Nutrition 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000010668 complexation reaction Methods 0.000 claims abstract description 13
- 238000011033 desalting Methods 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 230000002776 aggregation Effects 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 38
- 238000006317 isomerization reaction Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000004064 recycling Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000001179 sorption measurement Methods 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000005054 agglomeration Methods 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000004220 aggregation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 62
- 239000003729 cation exchange resin Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000003957 anion exchange resin Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 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
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
Abstract
The invention discloses a preparation method of lactulose, which comprises the following steps: s1, preparing lactose solution; s2, adding boric acid into the lactose solution of the S1, and isomerizing lactose by the reaction solution; s3, adding acid to remove complexation of tetrahydroxy boron ions and lactulose; s4, mannitol is added into the solution of the S2, and the mannitol and boron form a complex; s5, adding graphene oxide uniformly dispersed in deionized water; with stirring, hydroxyl groups on the surface of the flaky graphene oxide and mannitol-boron complex and tetrahydroxy boron ions form hydrogen bond connection to form aggregation; filtering and separating the graphene oxide agglomerates captured with boron; s6, sequentially desalting the graphene oxide-boron removed material and removing non-isomerized lactose to obtain target lactulose; the invention utilizes boric acid to selectively complex to prepare the isomerized lactose, and simultaneously effectively recovers the boric acid, thereby reducing the separation cost of the boron.
Description
Technical Field
The invention relates to the technical field of lactulose preparation, in particular to a preparation method of lactulose.
Background
Chemical isomerism is a common way of producing lactuloseUnder alkaline conditions, the reducing lactose is subjected to heat treatment, and the glucose on lactose units is subjected to LA rearrangement and is directly isomerized into fructose, so that lactulose is produced. The basic catalysts used in chemical isomerism are of a variety of types including NaOH and Ca (OH) 2 Tertiary amines of strong organic bases as complex catalysts, e.g. Al 2 O 3 And Na (Na) 2 CO 3 Tertiary amine complex boric acid and H 3 BO 3 /NaOH、NaAlO 2 Complex nature catalysts such as systems.
The prior art has the problems that a large amount of soluble catalyst is used, so that side reactions are easy to occur, a reaction system contains a large amount of salt, and the separation and purification difficulty of lactulose is increased.
Disclosure of Invention
The invention aims to provide a preparation method of lactulose, which utilizes boric acid to selectively complex to prepare isomerized lactose, and simultaneously effectively recovers boric acid and reduces the separation cost of boron.
In order to solve the technical problem, the technical scheme of the invention is as follows: a method for preparing lactulose, comprising the following steps:
s1, preparing lactose solution with lactose concentration of (30 g to 50 g)/100 ml;
s2, adding boric acid into the lactose solution of S1, wherein the dosage of the boric acid is (4 g to 5 g)/100 ml;
lactose isomerization is carried out on the reaction solution, and the process conditions of the isomerization are as follows:
lactose solution pH 9 to 11;
the reaction temperature is 70 ℃ to 90 ℃;
the reaction time is 100min to 140min;
s3, adding acid into the isomerised reaction solution of S2 to adjust the pH value of the solution to 2.2-2.8, and removing complexation of tetrahydroxy boron ions and lactulose;
s4, mannitol is added into the solution of the S2, and the mannitol and boron form a complex;
s5, adding graphene oxide uniformly dispersed in deionized water into the material passing through the step S4 step by step for multiple times;
with stirring, hydroxyl groups on the surface of the flaky graphene oxide form hydrogen bond connection with mannitol-boron complex and tetrahydroxy boron ions, and the flaky graphene oxide is bonded to capture mannitol-boron complex and tetrahydroxy boron ions and further contacts with surrounding flaky graphene oxide connected with mannitol-boron complex and tetrahydroxy boron ions to generate agglomeration;
filtering and separating the graphene oxide agglomerates captured with boron;
s6, sequentially desalting the graphene oxide-boron removed material and removing non-isomerized lactose to obtain target lactulose;
the material passing through S5 is subjected to ion exchange resin to remove salt and boron is removed by primary boron selective adsorption resin.
Preferably, the mass ratio of graphene oxide to boric acid is (2.1 to 2.2): 1. the method ensures that the graphene oxide effectively captures boric acid.
Preferably, the recovery of the S5 separated and collected graphene oxide-mannitol-boron complex and graphene oxide-tetrahydroxy boron ion comprises the following steps:
s51, cleaning the graphene oxide-mannitol-boron complex and graphene oxide-tetrahydroxy boron ions, and drying;
s52, placing the graphene oxide-mannitol-boron complex obtained in the S51 and graphene oxide-tetrahydroxy boron ions under inert gas for heat treatment, and converting boron in the mannitol-boron complex and the tetrahydroxy boron ions into B2O3 after losing water molecules;
S53、B 2 O 3 melting in the heating process; at the same time, the oxygen-containing functional groups of graphene oxide decompose to produce water molecules and carbon dioxide, and the molten boron bonds to the graphene.
In the invention, tetrahydroxy boron ions complexed with graphene oxide are intercalated into graphene oxide in the heating process.
The recovered part of graphene oxide/graphene is doped with B or is bonded with graphene oxide/graphene to be connected with B 2 O 3 Effectively ensures the constancy of B, in order to further ensure the completion of the obtained B elementFully effective utilization of graphene oxide and graphene and B 2 O 3 Grinding the mixture of the graphene and the boric acid crystal, raising the temperature of the heat treatment of S52 to 800-1000 ℃, decomposing and reducing the oxygen-containing groups of partial oxidized graphene into graphene, and quenching the mixture of the graphene and the boric acid crystal to a molten state at high temperature, wherein with the heat preservation, boron atoms are diffused and connected with the graphene and the graphene to form a lamellar structure to form reusable graphene-B 2 O 3 Is connected with the graphene-B 2 O 3 The catalyst of (2) is separated by alcohol washing to realize graphene-B 2 O 3 The catalyst is reused directly.
To improve graphene-B 2 O 3 The catalytic performance of the catalyst can be added with B according to actual needs 2 O 3 Improving the catalytic performance of the catalyst.
The preferable process conditions for the S52 heat treatment are:
an Ar gas atmosphere;
the temperature is 680 ℃ to 750 ℃;
the time is 3 hours to 6 hours.
Preferably, graphene-B prepared from S53 2 O 3 Putting into lactose solution of S1, and graphene-B 2 O 3 Conversion to graphene-B (OH) 4 - Can be used as a catalyst for lactose isomerization for recycling. The method effectively realizes the recycling of the boric acid by utilizing the bonding capture of the graphene oxide and the boric acid, and does not influence the repeated use of the boric acid.
Preferably, the target lactose solution obtained in the step S6 is concentrated to 70-80% of concentration under reduced pressure at 55-75 ℃, cooled to 45 ℃, added with seed crystal, naturally cooled, stirred and crystallized, the stirring speed is 30 revolutions per minute, crystallized for 24 hours, and centrifuged to obtain lactulose solid.
The invention separates tetrahydroxy boron ions from the isomerization reaction system, thereby facilitating the subsequent purification of lactulose.
Preferably, the S6 desalting is to subject the material subjected to S5 to desalting by an ion exchange resin and to desalting by a primary boron selective adsorption resin, wherein sulfuric acid for eliminating boric acid-lactulose complexation is included.
Preferably, the sulfuric acid recovered by the S6 is led into the S3 for recycling. The invention realizes the recycling of sulfuric acid and reduces the use of acidic substances.
The preferred method for removing non-isomerized lactose in S6 is as follows:
s61, respectively introducing the materials subjected to S5 into a first group of moving beds to separate lactose;
s62, introducing the material subjected to S61 into a second group of moving beds to separate the mixed sugar;
obtaining the target lactulose.
Preferably, the mode of filtration of the graphene oxide agglomerates having captured mannitol-boron complexes and tetrahydroxy boron ions is suction filtration. According to the invention, the relative flow velocity between graphene oxide and boron is delayed by utilizing aggregation of flaky graphene oxide in the suction filtration process, more tetrahydroxy boron ions or mannitol-boron complex are promoted to flow through the surface of the graphene oxide, the relative distance between two substances with hydrogen bond interaction is shortened, the formation of hydrogen bonds is easier, and the graphene oxide effectively captures boron.
By adopting the technical scheme, the invention has the beneficial effects that:
the invention uses boric acid as a catalyst for lactose isomerization, utilizes boric acid and lactulose to form a complex to effectively inhibit side reaction, and the lactulose molecule contains a furan six-membered ring and a pyran six-membered ring, and has cis-di-ortho-hydroxyl in the furan ring, and the complex with tetrahydroxy boron ions occurs under alkaline environment, and the principle of the complex is as follows:
the tetrahydroxy boron ions effectively capture the isomerized lactulose, so that the forward reaction degree of the lactulose is improved; however, the problem in the prior art is that boric acid is difficult to separate in the reacted materials, separation by resin is needed, separation by resin is similar to filtration, and resin has a certain limit on acid tolerance of solution, so in the process of adsorbing boron by resin, in order to protect the resin, the pH value of the materials is more than 3.0, and a part of boron is complexed with lactulose, so that the separation of lactulose is affected and boron pollution is easily caused.
Under the catalysis of alkali, when lactose isomerization is completed, tetrahydroxy boron ions are complexed with lactulose, acid is added into a material system after reaction, the pH value of a liquid environment is regulated to be 2.2-2.8, and the complexes of the tetrahydroxy boron ions and the lactulose are fully separated; at the moment, graphene oxide uniformly dispersed in deionized water is added into a system, and with stirring, GO has sufficient hydroxyl on the surface, GO is of a lamellar structure to form a similar net structure to capture tetrahydroxy boron ions in a liquid environment, but the tetrahydroxy boron ions are reversely hydrolyzed to be converted into boric acid due to the pH value of the system being 2.2-2.8, namely, the tetrahydroxy boron ions cannot be singly utilized to directly form hydrogen bonds with the graphene oxide, so mannitol is added into the system while acid is added for removing complexation, and the following complexation reaction occurs between the boric acid and the mannitol in the dynamic process of removing complexation of the tetrahydroxy boron ions by using mannitol;
aiming at the existence of the mannitol-boron complex, graphene oxide and tetrahydroxy boron ions directly form hydrogen bonds or graphene oxide and the mannitol-boron complex form connection through the hydrogen bonds of mannitol; the boron is captured by the flaky GO, the GO capturing the boron continuously captures surrounding graphene oxide capturing the boron through mannitol-boron complex or tetrahydroxy boron ions, and the originally dispersed graphene oxide is obviously agglomerated along with stirring because the capturing boron is equivalent to the further increase of the hydroxyl number on the surface of the graphene oxide;
according to the invention, the graphene oxide captures and enriches boron and is separated from the system, the graphene oxide is distributed in the whole liquid environment to capture micro-areas, the separation is thorough, and the graphene oxide is easy to filter and separate from the system;
wherein mannitol used for complexing with boron is decomposed and removed in the high-temperature treatment process, and the recovered B can be circularly put into lactose isomerization reaction for recycling;
the invention uses the bonding of the graphene oxide and the boric acid under the acidity to facilitate the recovery of the boric acid on the premise of using the boric acid to improve the lactulose conversion rate and inhibit side reactions.
Detailed Description
In order to further explain the technical scheme of the invention, the invention is explained in detail by specific examples.
Example 1
The embodiment discloses a preparation method of lactulose, which comprises the following steps:
s1, preparing lactose solution with the concentration of 30g/100 ml;
s2, adding boric acid into the lactose solution of S1, wherein the adding amount is 4g/100ml; lactose isomerization reaction is carried out on the solution, and the isomerization process conditions are as follows:
lactose solution pH value is 9;
the reaction temperature is 70 ℃;
the reaction time is 100min;
s3, adding acid into the isomerized reaction solution of the S2 to adjust the pH value of the solution to 2.2, and removing complexation of tetrahydroxy boron ions and lactulose;
s4, adding mannitol into the solution of the S2 while adding acid, wherein the mannitol and boron form a complex; mannitol is used in an amount of 3g/100ml;
s5, adding graphene oxide uniformly dispersed in deionized water into the material passing through the step S4 step by step for multiple times;
graphene oxide 8.4g/100ml.
With stirring, hydroxyl groups on the surface of the flaky graphene oxide form hydrogen bond connection with mannitol-boron complex and tetrahydroxy boron ions, and the flaky graphene oxide is bonded to capture mannitol-boron complex and tetrahydroxy boron ions and further contacts with surrounding flaky graphene oxide connected with mannitol-boron complex and tetrahydroxy boron ions to generate agglomeration;
recovering S5 the graphene oxide-mannitol-boron complex and the graphene oxide-tetrahydroxy boron ion which are separated and collected comprises the following steps:
s51, cleaning the graphene oxide-mannitol-boron complex and graphene oxide-tetrahydroxy boron ions, and drying;
s52, placing the graphene oxide-mannitol-boron complex obtained in S51 and graphene oxide-tetrahydroxy boron ions under inert gas for heat treatment, and converting the boron in the mannitol-boron complex and the tetrahydroxy boron ions into B after losing water molecules 2 O 3 ；
The process conditions of the S52 heat treatment are as follows:
an Ar gas atmosphere;
the temperature is 720 ℃;
the time was 4 hours.
S53、B 2 O 3 Melting in the heating process; at the same time, the oxygen-containing functional groups of graphene oxide decompose to produce water molecules and carbon dioxide, and the molten boron bonds to the graphene.
Filtering and separating graphene oxide agglomerates captured with mannitol-boron complex and tetrahydroxy boron ions;
graphene-B prepared by S53 2 O 3 Putting into lactose solution of S1, and graphene-B 2 O 3 Conversion to graphene-B (OH) 4 - Can be used as a catalyst for lactose isomerization for recycling.
S6, respectively desalting the material from which the mannitol-boron complex is removed and removing non-isomerized lactose to obtain the target lactulose.
S6, introducing the GO capturing and boron removing material into an anion exchange resin column and a cation exchange resin column to remove sodium sulfate, and removing boron by using a boron selective adsorption resin;
thereafter, the non-isomerized lactose was removed to obtain the objective lactulose.
The sulfuric acid recovered by the S6 is led into the S3 for recycling.
The method for removing non-isomerized lactose in S6 is as follows:
s61, respectively introducing the materials subjected to S5 into a first group of moving beds to separate lactose;
s62, introducing the material subjected to S61 into a second group of moving beds to separate the mixed sugar;
obtaining the target lactulose.
Concentrating the target lactose solution obtained in the step S5 under reduced pressure at 55 ℃ until the concentration is 70%, cooling to 45 ℃, adding seed crystals, naturally cooling, stirring for crystallization, stirring for 30 r/min, crystallizing for 24 hours, and centrifuging to obtain lactulose solid.
Example 2
The embodiment discloses a preparation method of lactulose, which comprises the following steps:
s1, preparing a lactose solution with the concentration of 40g/100 ml;
s2, adding boric acid into the lactose solution of the S1, wherein the adding amount is 5g/100ml; lactose isomerization reaction is carried out on the solution, and the isomerization process conditions are as follows:
lactose solution pH value is 10;
the reaction temperature is 70 ℃;
the reaction time is 120min;
s3, adding acid into the isomerized reaction solution of the S2 to adjust the pH value of the solution to 2.4, and removing complexation of tetrahydroxy boron ions and lactulose;
s4, adding mannitol into the solution of the S2 while adding acid, wherein the mannitol and boron form a complex; mannitol is used in an amount of 3.3g/100ml;
s5, adding graphene oxide uniformly dispersed in deionized water into the material passing through the step S4 step by step for multiple times; 11g/100ml graphene oxide.
With stirring, hydroxyl groups on the surface of the flaky graphene oxide form hydrogen bond connection with mannitol-boron complex and tetrahydroxy boron ions, and the flaky graphene oxide is bonded to capture mannitol-boron complex and tetrahydroxy boron ions and further contacts with surrounding flaky graphene oxide connected with mannitol-boron complex and tetrahydroxy boron ions to generate agglomeration;
recovering S5 the graphene oxide-mannitol-boron complex and the graphene oxide-tetrahydroxy boron ion which are separated and collected comprises the following steps:
s51, cleaning the graphene oxide-mannitol-boron complex and graphene oxide-tetrahydroxy boron ions, and drying;
s52, placing the graphene oxide-mannitol-boron complex obtained in S51 and graphene oxide-tetrahydroxy boron ions under inert gas for heat treatment, and converting the boron in the mannitol-boron complex and the tetrahydroxy boron ions into B after losing water molecules 2 O 3 ；
The process conditions of the S52 heat treatment are as follows:
an Ar gas atmosphere;
the temperature is 680 ℃;
the time was 3 hours.
S53、B 2 O 3 Melting in the heating process; at the same time, the oxygen-containing functional groups of graphene oxide decompose to produce water molecules and carbon dioxide, and the molten boron bonds to the graphene.
Filtering and separating graphene oxide agglomerates captured with mannitol-boron complex and tetrahydroxy boron ions;
graphene-B prepared by S53 2 O 3 Putting into lactose solution of S1, and graphene-B 2 O 3 Conversion to graphene-B (OH) 4 - Can be used as a catalyst for lactose isomerization for recycling.
S6, respectively desalting the material from which the mannitol-boron complex is removed and removing non-isomerized lactose to obtain the target lactulose.
S6, introducing the GO capturing and boron removing material into an anion exchange resin column and a cation exchange resin column to remove sodium sulfate, and removing boron by using a boron selective adsorption resin;
thereafter, the non-isomerized lactose was removed to obtain the objective lactulose.
The sulfuric acid recovered by the S6 is led into the S3 for recycling.
The method for removing non-isomerized lactose in S6 is as follows:
s61, respectively introducing the materials subjected to S5 into a first group of moving beds to separate lactose;
s62, introducing the material subjected to S61 into a second group of moving beds to separate the mixed sugar;
obtaining the target lactulose.
Concentrating the target lactose solution obtained in the step S5 under reduced pressure at 65 ℃ until the concentration is 80%, cooling to 45 ℃, adding seed crystals, naturally cooling, stirring for crystallization, stirring for 30 r/min, crystallizing for 24 hours, and centrifuging to obtain lactulose solid.
Example 3
The embodiment discloses a preparation method of lactulose, which comprises the following steps:
s1, preparing 50g/100ml lactose solution;
s2, adding boric acid into the lactose solution of S1, wherein the adding amount is 4g/100ml; lactose isomerization reaction is carried out on the solution, and the isomerization process conditions are as follows:
lactose solution pH value is 11;
the reaction temperature is 70 ℃;
the reaction time is 140min;
s3, adding acid into the isomerized reaction solution of the S2 to adjust the pH value of the solution to 2.6, and removing complexation of tetrahydroxy boron ions and lactulose;
s4, adding mannitol into the solution of the S2 while adding acid, wherein the mannitol and boron form a complex; mannitol is used in an amount of 3.1g/100ml;
s5, adding graphene oxide uniformly dispersed in deionized water into the material passing through the step S4 step by step for multiple times;
graphene oxide 8.8g/100ml.
With stirring, hydroxyl groups on the surface of the flaky graphene oxide form hydrogen bond connection with mannitol-boron complex and tetrahydroxy boron ions, and the flaky graphene oxide is bonded to capture mannitol-boron complex and tetrahydroxy boron ions and further contacts with surrounding flaky graphene oxide connected with mannitol-boron complex and tetrahydroxy boron ions to generate agglomeration;
recovering S5 the graphene oxide-mannitol-boron complex and the graphene oxide-tetrahydroxy boron ion which are separated and collected comprises the following steps:
s51, cleaning the graphene oxide-mannitol-boron complex and graphene oxide-tetrahydroxy boron ions, and drying;
s52, placing the graphene oxide-mannitol-boron complex obtained in S51 and graphene oxide-tetrahydroxy boron ions under inert gas for heat treatment, and converting the boron in the mannitol-boron complex and the tetrahydroxy boron ions into B after losing water molecules 2 O 3 ；
The process conditions of the S52 heat treatment are as follows:
an Ar gas atmosphere;
the temperature is 750 ℃;
the time was 6 hours.
S53、B 2 O 3 Melting in the heating process; at the same time, the oxygen-containing functional groups of graphene oxide decompose to produce water molecules and carbon dioxide, and the molten boron bonds to the graphene.
Filtering and separating graphene oxide agglomerates captured with mannitol-boron complex and tetrahydroxy boron ions;
graphene-B prepared by S53 2 O 3 Putting into lactose solution of S1, and graphene-B 2 O 3 Conversion to graphene-B (OH) 4 - As lactose isomerisationThe catalyst is recycled.
S6, introducing the GO capturing and boron removing material into an anion exchange resin column and a cation exchange resin column to remove sodium sulfate, and removing boron by using a boron selective adsorption resin;
thereafter, the non-isomerized lactose was removed to obtain the objective lactulose.
The sulfuric acid recovered by the S6 is led into the S3 for recycling.
The method for removing non-isomerized lactose in S6 is as follows:
s61, respectively introducing the materials subjected to S5 into a first group of moving beds to separate lactose;
s62, introducing the material subjected to S61 into a second group of moving beds to separate the mixed sugar;
obtaining the target lactulose.
Concentrating the target lactose solution obtained in the step S6 under reduced pressure at 75 ℃ until the concentration is 70%, cooling to 45 ℃, adding seed crystals, naturally cooling, stirring for crystallization, stirring for 30 r/min, crystallizing for 24 hours, and centrifuging to obtain lactulose solid.
Example 4
The embodiment discloses a preparation method of lactulose, which comprises the following steps:
s1, preparing a lactose solution with the concentration of 40g/100 ml;
s2, adding boric acid into the lactose solution of the S1, wherein the adding amount is 5g/100ml; lactose isomerization reaction is carried out on the solution, and the isomerization process conditions are as follows:
lactose solution pH 10
The reaction temperature is 80 ℃;
the reaction time is 100min;
s3, adding acid into the isomerized reaction solution of the S2 to adjust the pH value of the solution to 2.8, and removing complexation of tetrahydroxy boron ions and lactulose;
s4, adding mannitol into the solution of the S2 while adding acid, wherein the mannitol and boron form a complex; mannitol is used in an amount of 3.6g/100ml;
s5, adding graphene oxide uniformly dispersed in deionized water into the material passing through the step S4 step by step for multiple times;
graphene oxide 10.5g/100ml.
With stirring, hydroxyl groups on the surface of the flaky graphene oxide form hydrogen bond connection with mannitol-boron complex and tetrahydroxy boron ions, and the flaky graphene oxide is bonded to capture mannitol-boron complex and tetrahydroxy boron ions and further contacts with surrounding flaky graphene oxide connected with mannitol-boron complex and tetrahydroxy boron ions to generate agglomeration;
recovering S5 the graphene oxide-mannitol-boron complex and the graphene oxide-tetrahydroxy boron ion which are separated and collected comprises the following steps:
s51, cleaning the graphene oxide-mannitol-boron complex and graphene oxide-tetrahydroxy boron ions, and drying;
s52, placing the graphene oxide-mannitol-boron complex obtained in S51 and graphene oxide-tetrahydroxy boron ions under inert gas for heat treatment, and converting the boron in the mannitol-boron complex and the tetrahydroxy boron ions into B after losing water molecules 2 O 3 ；
The process conditions of the S52 heat treatment are as follows:
an Ar gas atmosphere;
the temperature is 750 ℃;
the time was 4 hours.
S53、B 2 O 3 Melting in the heating process; at the same time, the oxygen-containing functional groups of graphene oxide decompose to produce water molecules and carbon dioxide, and the molten boron bonds to the graphene.
Filtering and separating graphene oxide agglomerates captured with mannitol-boron complex and tetrahydroxy boron ions;
graphene-B prepared by S53 2 O 3 Putting into lactose solution of S1, and graphene-B 2 O 3 Conversion to graphene-B (OH) 4 - Can be used as a catalyst for lactose isomerization for recycling.
S6, respectively desalting the material from which the mannitol-boron complex is removed and removing non-isomerized lactose to obtain the target lactulose.
S6, introducing the GO capturing and boron removing material into an anion exchange resin column and a cation exchange resin column to remove sodium sulfate, and removing boron by using a boron selective adsorption resin;
thereafter, the non-isomerized lactose was removed to obtain the objective lactulose.
The sulfuric acid recovered by the S6 is led into the S3 for recycling.
The method for removing non-isomerized lactose in S6 is as follows:
s61, respectively introducing the materials subjected to S5 into a first group of moving beds to separate lactose;
s62, introducing the material subjected to S61 into a second group of moving beds to separate the mixed sugar;
obtaining the target lactulose.
Concentrating the target lactose solution obtained in the step S6 under reduced pressure at 55 ℃ until the concentration is 80%, cooling to 45 ℃, adding seed crystals, naturally cooling, stirring for crystallization, stirring for 30 r/min, crystallizing for 24 hours, and centrifuging to obtain lactulose solid.
Example 5
The embodiment discloses a preparation method of lactulose, which comprises the following steps:
s1, preparing lactose solution with the concentration of 30g/100 ml;
s2, adding boric acid into the lactose solution of S1, wherein the adding amount is 4g/100ml; the solution is subjected to lactose isomerization reaction,
the process conditions for isomerization are as follows:
lactose solution pH value is 9;
the reaction temperature is 90 ℃;
the reaction time is 120min;
s3, adding acid into the isomerized reaction solution of the S2 to adjust the pH value of the solution to 2.8, and removing complexation of tetrahydroxy boron ions and lactulose;
s4, adding mannitol into the solution of the S2 while adding acid, wherein the mannitol and boron form a complex; mannitol is used in an amount of 3.0g/100ml;
s5, adding graphene oxide uniformly dispersed in deionized water into the material passing through the step S4 step by step for multiple times;
graphene oxide 8.4g/100ml.
With stirring, hydroxyl groups on the surface of the flaky graphene oxide form hydrogen bond connection with mannitol-boron complex and tetrahydroxy boron ions, and the flaky graphene oxide is bonded to capture mannitol-boron complex and tetrahydroxy boron ions and further contacts with surrounding flaky graphene oxide connected with mannitol-boron complex and tetrahydroxy boron ions to generate agglomeration;
recovering S5 the graphene oxide-mannitol-boron complex and the graphene oxide-tetrahydroxy boron ion which are separated and collected comprises the following steps:
s51, cleaning the graphene oxide-mannitol-boron complex and graphene oxide-tetrahydroxy boron ions, and drying;
s52, placing the graphene oxide-mannitol-boron complex obtained in S51 and graphene oxide-tetrahydroxy boron ions under inert gas for heat treatment, and converting the boron in the mannitol-boron complex and the tetrahydroxy boron ions into B after losing water molecules 2 O 3 ；
The process conditions of the S52 heat treatment are as follows:
an Ar gas atmosphere;
the temperature is 720 ℃;
the time was 6 hours.
S53、B 2 O 3 Melting in the heating process; at the same time, the oxygen-containing functional groups of graphene oxide decompose to produce water molecules and carbon dioxide, and the molten boron bonds to the graphene.
Filtering and separating graphene oxide agglomerates captured with mannitol-boron complex and tetrahydroxy boron ions;
graphene-B prepared by S53 2 O 3 Putting into lactose solution of S1, and graphene-B 2 O 3 Conversion to graphene-B (OH) 4 - Can be used as a catalyst for lactose isomerization for recycling.
S6, respectively desalting the material from which the mannitol-boron complex is removed and removing non-isomerized lactose to obtain the target lactulose.
S6, introducing the GO capturing and boron removing material into an anion exchange resin column and a cation exchange resin column to remove sodium sulfate, and removing boron by using a boron selective adsorption resin;
thereafter, the non-isomerized lactose was removed to obtain the objective lactulose.
The sulfuric acid recovered by the S6 is led into the S3 for recycling.
The method for removing non-isomerized lactose in S6 is as follows:
s61, respectively introducing the materials subjected to S5 into a first group of moving beds to separate lactose;
s62, introducing the material subjected to S61 into a second group of moving beds to separate the mixed sugar;
obtaining the target lactulose.
Concentrating the target lactose solution obtained in the step S6 under reduced pressure at 65 ℃ until the concentration is 70%, cooling to 45 ℃, adding seed crystals, naturally cooling, stirring for crystallization, stirring for 30 r/min, crystallizing for 24 hours, and centrifuging to obtain lactulose solid.
Comparative example
The preparation method of lactulose disclosed by CN113150042B is adopted in the comparative example, and the specific production method is as follows:
lactose isomerisation solution and isomerisation process conditions are the same as in example 1, specifically as follows:
s1, preparing lactose solution with the concentration of 30g/100 ml;
s2, adding boric acid into the lactose solution of S1, wherein the adding amount is 4g/100ml; the solution is subjected to lactose isomerization reaction,
the process conditions for isomerization are as follows:
lactose solution pH value is 9;
the reaction temperature is 70 ℃;
the reaction time is 100min;
the obtained material is concentrated and purified by ion exchange, and the specific method is as follows:
pumping lactulose reaction liquid (30L) from a storage tank into a resin column of a first cation exchange resin, a second boron selective adsorption resin, a third boron selective adsorption resin, a fourth boron selective adsorption resin, a fifth cation exchange resin and a sixth boron selective adsorption resin in sequence through a pump, and eluting the tree with purified water in sequence after the reaction liquid is finishedA fat column, controlling the elution flow rate of the sixth boron selective adsorption resin column to be 2 BV/h; collecting effluent from the sixth boron selective adsorption resin column, and having a density of 1.001-1.200g/cm according to a conductivity of less than 10 μs/cm (20deg.C) 3 Is used for collecting qualified components.
Indirect determination of boron concentration C in S5 lactulose feed solutions in examples 1 to 5 by flame atomic absorption spectrometry 0 Examples 1 to 5 boron content in lactulose solution before concentration after desalting vs. the concentration of boron in the lactulose solution obtained in the comparative example was C f Specific test data are shown in table 1.
Table 1 boron content of examples 1 to 5 and comparative examples
| Project | C GO | C f |
| Example 1 | 68ppm | 1.4ppm |
| Example 2 | 72ppm | 1.5ppm |
| Example 3 | 67ppm | 1.3ppm |
| Example 4 | 74ppm | 1.6ppm |
| Example 5 | 66ppm | 1.3ppm |
| Comparative example | / | 1.2ppm |
As can be seen from the data in table 1, the method utilizes the graphene oxide to capture and enrich boron and separate the boron from the system, and the graphene oxide is distributed in the whole liquid environment to capture micro-areas, so that the separation is thorough and the filtration and separation from the system are easy; mannitol used for complexing with boron is decomposed and removed in the high-temperature treatment process, so that the obtained graphene-B is conveniently put into lactose isomerization for recycling; on the premise of improving the lactulose conversion rate and inhibiting side reactions by using boric acid, the bonding between the graphene oxide and the boric acid is convenient for recycling the boric acid, and the boron removal method has a boron removal effect similar to that of a process of removing boron by using boron selective adsorption resin repeatedly.
Claims (10)
1. A preparation method of lactulose is characterized in that: the method comprises the following steps:
s1, preparing lactose solution with lactose concentration of (30 g to 50 g)/100 ml;
s2, adding boric acid into the lactose solution of S1, wherein the dosage of the boric acid is (4 g to 5 g)/100 ml;
lactose isomerization is carried out on the reaction solution, and the process conditions of the isomerization are as follows:
lactose solution pH 9 to 11;
the reaction temperature is 70 ℃ to 90 ℃;
the reaction time is 100min to 140min;
s3, adding acid into the isomerised reaction solution of S2 to adjust the pH value of the solution to 2.2-2.8, and removing complexation of tetrahydroxy boron ions and lactulose;
s4, mannitol is added into the solution of the S2, and the mannitol and boron form a complex;
s5, adding graphene oxide uniformly dispersed in deionized water into the material passing through the step S4 step by step for multiple times;
with stirring, hydroxyl groups on the surface of the flaky graphene oxide form hydrogen bond connection with mannitol-boron complex and tetrahydroxy boron ions, and the flaky graphene oxide is bonded to capture mannitol-boron complex and tetrahydroxy boron ions and further contacts with surrounding flaky graphene oxide connected with mannitol-boron complex and tetrahydroxy boron ions to generate agglomeration;
filtering and separating the graphene oxide agglomerates captured with boron;
s6, sequentially desalting the graphene oxide-boron removed material and removing non-isomerized lactose to obtain target lactulose;
the desalting in S6 is to subject the material passing through S5 to the desalting through ion exchange resin and the boron removing through primary boron selective adsorption resin.
2. The method of manufacturing according to claim 1, characterized in that:
the mass ratio of graphene oxide to boric acid is (2.1 to 2.2): 1.
3. the method of manufacturing according to claim 1, characterized in that: recovering S5 the graphene oxide-mannitol-boron complex and the graphene oxide-tetrahydroxy boron ion which are separated and collected comprises the following steps:
s51, cleaning the graphene oxide-mannitol-boron complex and graphene oxide-tetrahydroxy boron ions, and drying;
s52, placing the graphene oxide-mannitol-boron complex obtained in S51 and graphene oxide-tetrahydroxy boron ions under inert gas for heat treatment, and converting the boron in the mannitol-boron complex and the tetrahydroxy boron ions into B after losing water molecules 2 O 3 ；
S53、B 2 O 3 Melting in the heating process; at the same time, the oxygen-containing functional groups of graphene oxide decompose to produce water molecules and carbon dioxide, and the molten boron bonds to the graphene.
4. A method of preparation according to claim 3, characterized in that: the process conditions of the S52 heat treatment are as follows:
an Ar gas atmosphere;
the temperature is 680 ℃ to 750 ℃;
the time is 3 hours to 6 hours.
5. A method of preparation according to claim 3, characterized in that:
graphene-B prepared by S53 2 O 3 Putting into lactose solution of S1, and graphene-B 2 O 3 Conversion to graphene-B (OH) 4 - Can be used as a catalyst for lactose isomerization for recycling.
6. The method of manufacturing according to claim 1, characterized in that: concentrating the target lactulose solution obtained in the step S6 at 55-75 ℃ under reduced pressure until the concentration is 70-80%, cooling to 45 ℃, adding seed crystals, naturally cooling, stirring for crystallization, stirring for 30 r/min, crystallizing for 24 h, and centrifuging to obtain lactulose solid.
7. The method of manufacturing according to claim 1, characterized in that: s6, removing salt through ion exchange to remove salt and recovering sulfuric acid for removing boric acid-lactulose complexation.
8. The method of manufacturing according to claim 7, wherein: and (3) introducing the sulfuric acid recovered in the step (S6) into the step (S3) for recycling.
9. The method of manufacturing according to claim 1, characterized in that: the method for removing non-isomerized lactose in S6 is as follows:
s61, respectively introducing the materials subjected to S5 into a first group of moving beds to separate lactose;
s62, introducing the material subjected to S61 into a second group of moving beds to separate the mixed sugar;
obtaining the target lactulose.
10. The method of manufacturing according to claim 1, characterized in that: the mode of filtration of the graphene oxide agglomerates captured with mannitol-boron complexes and tetrahydroxy boron ions is suction filtration.
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Denomination of invention: A method for preparing lactulose Granted publication date: 20231110 Pledgee: China Merchants Bank Co.,Ltd. Jinhua Branch Pledgor: SYNGARS TECHNOLOGY CO.,LTD. Registration number: Y2024980006636 |