CN114436768A - Method for recovering sorbitol and mannitol from mannitol mother liquor - Google Patents
Method for recovering sorbitol and mannitol from mannitol mother liquor Download PDFInfo
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- CN114436768A CN114436768A CN202111631875.8A CN202111631875A CN114436768A CN 114436768 A CN114436768 A CN 114436768A CN 202111631875 A CN202111631875 A CN 202111631875A CN 114436768 A CN114436768 A CN 114436768A
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- mannitol
- sorbitol
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- mother liquor
- moving bed
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- 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 title claims abstract description 129
- 235000010355 mannitol Nutrition 0.000 title claims abstract description 127
- 229930195725 Mannitol Natural products 0.000 title claims abstract description 125
- 239000000594 mannitol Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000012452 mother liquor Substances 0.000 title claims abstract description 44
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 title claims description 62
- 239000000600 sorbitol Substances 0.000 title claims description 62
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 title claims description 7
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 36
- 238000010828 elution Methods 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- 238000004042 decolorization Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000003957 anion exchange resin Substances 0.000 claims description 12
- 239000003729 cation exchange resin Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229910052755 nonmetal Inorganic materials 0.000 claims description 10
- 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 9
- 238000004255 ion exchange chromatography Methods 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 230000005526 G1 to G0 transition Effects 0.000 claims description 6
- 238000005374 membrane filtration Methods 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 238000001223 reverse osmosis Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 27
- 238000007670 refining Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 27
- 239000011575 calcium Substances 0.000 description 16
- 238000013375 chromatographic separation Methods 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 14
- 230000008025 crystallization Effects 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- 229910052791 calcium Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 235000021433 fructose syrup Nutrition 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 241001474374 Blennius Species 0.000 description 2
- RFSUNEUAIZKAJO-ZXXMMSQZSA-N alpha-D-fructofuranose Chemical compound OC[C@H]1O[C@@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ZXXMMSQZSA-N 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229960004903 invert sugar Drugs 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000845 maltitol Substances 0.000 description 1
- 235000010449 maltitol Nutrition 0.000 description 1
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 1
- 229940035436 maltitol Drugs 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process for separating mannitol mother liquor by simulated moving bed chromatography, which comprises the steps of crystallizing mannitol, generating the mother liquor, separating by the simulated moving bed chromatography, and pretreating and refining a separation solution. The method obviously improves the recovery utilization rate of the mannitol mother liquor, can be directly recycled and directly sold after separation, not only improves the added value of the mannitol mother liquor, but also creates considerable economic benefits for the mannitol project.
Description
Technical Field
The invention relates to the technical field of food processing, in particular to a method for recovering sorbitol and mannitol from mannitol mother liquor.
Background
Mannitol is a natural hexitol, widely exists in seaweed, fruits, plant leaves and the like, and is widely used in the fields of medicines, foods, chemical industry and the like at present due to the characteristics of no hygroscopicity, proper sweetness, low calorie, no decayed tooth, no toxic or side effect and the like. In recent years, with the development of science and technology, the production process of mannitol and the application in new fields are continuously expanded.
At present, methods for producing mannitol at home and abroad mainly comprise a seaweed extraction method, a chemical hydrogenation method, an electrochemical method and the like. The extraction method is mainly extracted from industrial waste materials for preparing iodine and sodium alginate, is a byproduct in iodine preparation industry, has low yield, complicated refining process and high production cost, and has no advantages in commercial production; the electrochemical method has not realized industrial production due to higher cost; whereas the chemical hydrogenation process is by far the predominant commercial production of mannitol. The chemical hydrogenation method mainly adopts the raw materials of crystalline fructose, sucrose invert sugar or high fructose syrup and the like to carry out hydrogenation production.
The biggest short plate of the prior mannitol manufacturing industry is the problem of recycling a large amount of mannitol mother liquor. Because the mannitol content of the mannitol mother liquor accounts for 13-15%, microcrystals are easily generated under low-temperature storage conditions, the mannitol mother liquor is not suitable for being directly used as the daily alcohol for external sale, most of the mannitol mother liquor is reused in the daily alcohol at the present stage, the optimal utilization value of a byproduct cannot be reflected, the mannitol content in the daily alcohol is high, the quality of the daily alcohol product is influenced, and the quality control is not facilitated. Therefore, a method for efficiently treating the mannitol mother liquor is urgently needed.
Disclosure of Invention
The invention aims to provide a process for separating mannitol mother liquor by simulated moving bed chromatography, which reduces the stock backlog of byproduct mannitol mother liquor, improves the recovery rate of mannitol mother liquor, and can create considerable economic benefit for mannitol projects while increasing the additional value of mannitol mother liquor.
The inventor team adopts starch liquefaction, saccharification, isomerization and chromatographic separation technologies to produce F90 high fructose syrup as a raw material, hydrogenation reaction is carried out under the conditions of high temperature and high pressure, a metal catalyst and hydrogen, beta-fructose in the raw material is converted into mannitol, alpha-fructose is converted into sorbitol, the contents of the beta-fructose and the alpha-fructose in the raw material respectively account for 40-50% after hydrogenation, and after refining, three times of crystallization and three times of separation are carried out to prepare a mannitol product. During the crystallization and separation of mannitol, a large amount of mannitol mother liquor is generated, 4 tons of mannitol mother liquor is generated per 1 ton of mannitol produced on average, and the yield of the product is low and only accounts for 20%.
F90 high fructose syrup is hydrogenated and converted into mannitol mixed solution, and D-mannitol with the purity of more than 99% is obtained by adopting three-stage crystallization and three-stage separation and purification processes, and meanwhile, mannitol mother liquor with a large amount of solid matters of 50-60% is separated and generated. Wherein, the components comprise 74.28 percent of sorbitol, 14.35 percent of mannitol, 1.32 percent of maltitol and 10.05 percent of other fusel.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided a method for recovering sorbitol and mannitol from a mannitol mother liquor, comprising the step of separating and recovering sorbitol and mannitol by a simulated moving bed chromatography system,
wherein, the stationary phase adopted by the simulated moving bed chromatographic system is strong acid styrene cation exchange resin.
Preferably, the ion type of the strong-acid styrene cation exchange resin is Ca+And (4) molding.
Preferably, the particle size of the strong-acid styrene cation exchange resin is 35-75 microns.
Preferably, the volume total exchange capacity of the strong-acid styrene cation exchange resin is 4.5-5.5 mmol/g.
Preferably, the wet apparent density of the strong-acid styrene cation exchange resin is 0.84-0.89 g/mL.
Specifically, ZGSPC106Ca, Monojet may be employedTM S1850、MonojetTM S1860、Amberlite CR1310Ca。
Preferably, the simulated moving bed chromatography system comprises 4-32 identical chromatography columns connected in series.
The simulated moving bed chromatographic system is used for separating mannitol, and has the characteristics of uniform particle size, high calcium type rate, good mechanical strength, strong pollution resistance and the like.
Further, the method according to the first aspect of the present invention comprises the steps of:
s1, continuously introducing a mannitol mother solution and an elution phase into a simulated moving bed chromatographic system, and respectively collecting a sorbitol solution and a mannitol solution from an extracting solution extraction point and a raffinate extraction point of the simulated moving bed chromatographic system;
and S2, respectively carrying out post-treatment on the collected sorbitol solution and mannitol solution to obtain a sorbitol product and a mannitol product.
Preferably, the elution phase in step S1 is water.
More preferably, deionized water, purified water, or degassed reverse osmosis water.
Preferably, the feed-liquid ratio of the mannitol mother liquor to the elution phase is (2-3): 1.
More preferably, the feed-liquid ratio of the mannitol mother liquor to the elution phase is (2.5-2.7): 1.
Further, according to the method of the first aspect of the present invention, the feed flow rate of the mannitol mother liquor in the step S1 is 3 to 4m3Preferably 3.1 to 3.5 m/h3/h；
The elution flow rate of the elution phase in the step S1 is 10.0-10.9 m3Preferably 10.2 to 10.6 m/h3/h；
The flow rate of the extracting solution in the step S1 is 5.50-6.50 m3Preferably 5.90 to 6.15 m/h3/h；
In the step S1, the flow rate of the raffinate is 7.20-8.10 m3Preferably 7.40 to 7.80 m/h3/h。
Further, according to the method of the first aspect of the present invention, the sorbitol solution is post-treated in step S2 by subjecting the sorbitol solution to decolorization, filtration, ion exchange chromatography, and evaporation to obtain the sorbitol product.
Preferably, the decolorization treatment is activated carbon decolorization for 30-60 min at 70-78 ℃,
more preferably, the decolorization treatment is activated carbon decolorization for 40min at 70-78 ℃;
preferably, the filtration is a pressure filtration,
more preferably, the filtration is plate and frame filter pressing;
preferably, the ion exchange chromatography is adsorption of metal and non-metal impurities through a cation and anion exchange resin column;
preferably, the evaporation is via a four-effect evaporator.
Specifically, 70% pharmaceutical grade 0270C sorbitol solution evaporated by a four-effect evaporator or 0270C sorbitol solution after evaporation is directly used for producing crystalline H20 or H60 sorbitol.
Further, according to the method of the first aspect of the present invention, the post-treatment method of the mannitol solution in step S2 is filtration, concentration, decolorization, and ion exchange chromatography to obtain the mannitol product.
Preferably, the filtration and concentration method is filtration through a three-stage membrane;
when the raw liquid flows through the membrane surface, the dense fine micropores only allow water and small molecular substances to pass through the membrane surface to form permeate, and substances with the volume larger than the micropore diameter of the membrane surface in the raw liquid are trapped on the liquid inlet side of the membrane to form concentrated liquid, so that the purposes of separating and concentrating the raw liquid are achieved.
Preferably, the decolorization treatment is activated carbon decolorization,
more preferably, the decolorization treatment is decolorization reaction at 70-78 ℃ for 30-60 min, and most preferably, the decolorization treatment is decolorization reaction with activated carbon at 70-78 ℃ for 40 min;
preferably, the ion exchange chromatography is adsorption of metallic and non-metallic impurities through a cation-anion exchange resin column.
Specifically, the prepared mannitol product is matched with mannitol mixed solution for use and can be repeatedly used for mannitol crystallization.
The invention has the beneficial effects that:
the invention provides a process for separating mannitol mother liquor by simulated moving bed chromatography, which comprises the steps of crystallizing mannitol, producing the mother liquor, separating by the simulated moving bed chromatography, and pretreating and refining a separation solution. The content of sorbitol in the mannitol mother liquor is improved to 98% by simulated moving bed chromatography separation, and the feed liquor can be directly sold as 0270C sorbitol liquid or used as a raw material of crystalline sorbitol for producing H20/H60 sorbitol after being refined. The content of mannitol is increased to 56%, which is similar to the quality index of mannitol crystallization raw material (mannitol mixed solution), and can be directly used for producing D-mannitol. The method obviously improves the recovery utilization rate of the mannitol mother liquor, can be directly recycled and directly sold after separation, not only improves the added value of the mannitol mother liquor, but also creates considerable economic benefits for the mannitol project.
Drawings
FIG. 1 is a schematic process flow diagram of a simulated moving bed chromatographic separation system.
FIG. 2 shows the specific parameter settings of the simulated moving bed chromatographic separation system.
Figure 3 is a specific frequency setting for process operation of a simulated moving bed chromatography separation system.
Figure 4 is a specific parameter setting of the process operation of the simulated moving bed chromatographic separation system.
Figure 5 is a specific frequency setting for process operation of a simulated moving bed chromatography separation system.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
A method for separating mannitol mother liquor by simulated moving bed chromatography comprises the following steps:
s1, continuously introducing a mannitol mother solution and an elution phase into a simulated moving bed chromatographic system, and respectively collecting a sorbitol solution and a mannitol solution from an extracting solution extraction point and a raffinate extraction point of the simulated moving bed chromatographic system;
and S2, respectively carrying out post-treatment on the collected sorbitol solution and mannitol solution to obtain a sorbitol product and a mannitol product.
The three-stage crystallization process of mannitol generates a large amount of mannitol mother liquor, and the components comprise 74.28% of sorbitol, 14.35% of mannitol and 52.0% of solids, and the raw material composition is used as feed data of simulated moving bed chromatographic separation.
The simulated moving bed chromatographic separation device adopts styrene strong acid primary color spectrum separation resin as a stationary phase, the ion type is calcium type, the calcium type rate is higher than 95%, the particle size is 35-75 micrometers, the total exchange capacity of the resin volume is 4.5-5.5 mmol/g, and the wet apparent density is 0.84-0.89 g/ml. The method is used for separating mannitol, and has the characteristics of uniform particle size, high calcium type rate, good mechanical strength, strong pollution resistance and the like. The elution phase is degassed reverse osmosis water, and is green, environment-friendly and pollution-free. The chromatographic resin selected in this example was ZGSPC106 Ca.
The system is operated in sections, each step has a reference time interval, and the total time interval is 4 time intervals, namely TA, TB, TC and TD. Each time interval has an accumulated flow for program switching, and when the accumulated amount is reached in the time interval, the system performs step switching. The 4 cumulative flow values are: VA, VB, VC and VD, when the accumulated value is reached, the system is switched, and a process flow chart is shown in attached figure 1.
Step A mainly has a separation effect, and circulating water is used for pushing the band to move backwards.
Step B is divided into 2 stages, one stage is water inlet and water outlet BD (raffinate), and the other stage is water inlet and water outlet AD (extract), wherein the water replenishing also has the effect of promoting the band movement.
And the step C and the step D are feeding and discharging stages, two products are simultaneously carried out, the occupied time is shortened, and a good separation effect is generated.
The specific parameters are shown in the following table 1, wherein the data correspond to the attached figure 2, the specific frequency setting is shown in the attached figure 3, the equilibrium parameters of the simulated moving bed chromatographic separation system are shown in the following table 2, and the quality indexes of the separated products are shown in the following table 3.
TABLE 1 simulated moving bed chromatography System specific operating parameters
TABLE 2 simulated moving bed chromatographic separation System equilibrium parameters
In practical applications, the feeding flow rate of the mannitol mother liquor in step S1 is generally set to 3-4 m3H is 3.1 to 3.5m3More preferably in the range of/h;
the elution flow rate of the elution phase is generally set to 10.0 to 10.9m3H is 10.2 to 10.6m3More preferably in the range of/h;
the flow rate of the extract is generally set to 5.50 to 6.50m3H is 5.90 to 6.15m3More preferably in the range of/h;
the flow rate of the raffinate is generally set at 7.20 to 8.10m3H is 7.40 to 7.80m3The range of the ratio of the carbon monoxide to the hydrogen is more preferable.
TABLE 3 quality index of the isolated product
HPLC patterns of the separated product are shown in figures 4 and 5, wherein the HPLC pattern of the AD material is shown in figure 4, and the analysis result table is shown in table 4; the HPLC profile of BD material is shown in FIG. 5, and the analysis results are shown in Table 5.
TABLE 4 HPLC-profiling result table for AD material
TABLE 5 BD materials HPLC chromatogram analysis results Table
According to the combined identification result, sorbitol in the components can be separated and purified from 70-75% to 95-99% as an AD material through the separation of mannitol mother liquor by simulated moving bed chromatography; the mannitol in the component is separated and purified from the content of 13-15% to 50-60% to be used as a BD material. The AD material is decolorized, filtered, ion exchanged and evaporated into pharmaceutical grade 0270C sorbitol solution or used as H20/H60 sorbitol raw material. The BD material is firstly subjected to three-stage membrane filtration to increase the concentration of the material liquid from 10-13% to 20-30%, and then subjected to multi-stage refining to be reused in mannitol mixed liquid for mannitol crystallization.
Subsequently, the separated product is further pretreated and refined:
(1) AD separating medium: the decolorizing temperature of the activated carbon is 70-78 ℃, the reaction time is 30-60 minutes, generally 40 minutes are selected, the activated carbon is filtered by a plate and frame filter, then the activated carbon is filtered by a cation-anion exchange resin column to adsorb metal and nonmetal impurities, and then the activated carbon is evaporated by a four-effect evaporator to obtain 70% medical grade 0270C sorbitol solution, and the 70% 0270C sorbitol solution can be continuously crystallized to be used for producing crystalline sorbitol, such as H20-H60 sorbitol.
(2) BD separation liquid: the method comprises the steps of firstly adopting three-stage membrane filtration to increase the concentration of feed liquid from 10-13% to 20-30%, then adsorbing metal and non-metal impurities through an activated carbon decoloration cation anion exchange resin column, and finally matching with mannitol mixed liquid for use to repeatedly use for mannitol crystallization. The decolorizing reaction is carried out for 30-60 min, generally 40min, at the decolorizing temperature of 70-78 ℃.
Example 2
A method for separating mannitol mother liquor by simulated moving bed chromatography comprises the following steps:
s1, continuously introducing a mannitol mother solution and an elution phase into a simulated moving bed chromatographic system, and respectively collecting a sorbitol solution and a mannitol solution from an extracting solution extraction point and a raffinate extraction point of the simulated moving bed chromatographic system;
and S2, respectively carrying out post-treatment on the collected sorbitol solution and mannitol solution to obtain a sorbitol product and a mannitol product.
The three-stage crystallization process of mannitol generates a large amount of mannitol mother liquor, and the components comprise 74.28% of sorbitol, 14.35% of mannitol and 52.0% of solids, and the raw material composition is used as feed data of simulated moving bed chromatographic separation.
The simulated moving bed chromatographic separation device adopts styrene strong acid primary color spectrum separation resin as a stationary phase, the ion type is calcium type, the calcium type rate is higher than 95%, the particle size is 35-75 micrometers, the total exchange capacity of the resin volume is 4.5-5.5 mmol/g, and the wet apparent density is 0.84-0.89 g/ml. The method is used for separating mannitol, and has the characteristics of uniform particle size, high calcium type rate, good mechanical strength, strong pollution resistance and the like. The elution phase is degassed reverse osmosis water, and is green, environment-friendly and pollution-free. The chromatographic resin selected in this example was MonojetTM S1850。
The system is operated in sections, each step has a reference time interval, and the total time interval is 4 time intervals, namely TA, TB, TC and TD. Each time interval has an accumulated flow for program switching, and when the accumulated amount is reached in the time interval, the system performs step switching. The 4 cumulative flow values are: VA, VB, VC and VD, when the accumulated value is reached, the system is switched, and a process flow chart is shown in attached figure 1.
Step A mainly has a separation effect, and circulating water is used for pushing the band to move backwards.
Step B is divided into 2 stages, one stage is water inlet and water outlet BD (raffinate), and the other stage is water inlet and water outlet AD (extract), wherein the water replenishing also has the effect of promoting the band movement.
And the step C and the step D are feeding and discharging stages, two products are simultaneously carried out, the occupied time is shortened, and a good separation effect is generated.
In practical applications, the feeding flow rate of the mannitol mother liquor in step S1 is generally set to 3-4 m3H is 3.1 to 3.5m3More preferably in the range of/h;
the elution flow rate of the elution phase is generally set to 10.0 to 10.9m3H is 10.2 to 10.6m3More preferably in the range of/h;
the flow rate of the extract is generally set to 5.50 to 6.50m3H is 5.90 to 6.15m3More preferably in the range of/h;
the flow rate of the raffinate is generally set at 7.20 to 8.10m3H is 7.40 to 7.80m3The range of the reaction time/h is more preferable.
Subsequently, the separated product is further pretreated and refined:
(1) AD separating medium: the decolorizing temperature of the activated carbon is 70-78 ℃, the reaction time is 30-60 minutes, generally 40 minutes are selected, the activated carbon is filtered by a plate and frame filter, then the activated carbon is filtered by a cation-anion exchange resin column to adsorb metal and nonmetal impurities, and then the activated carbon is evaporated by a four-effect evaporator to obtain 70% medical grade 0270C sorbitol solution, and the 70% 0270C sorbitol solution can be continuously crystallized to be used for producing crystalline sorbitol, such as H20-H60 sorbitol.
(2) BD separation liquid: the method comprises the steps of firstly adopting three-stage membrane filtration to increase the concentration of feed liquid from 10-13% to 20-30%, then adsorbing metal and non-metal impurities through an activated carbon decoloration cation anion exchange resin column, and finally matching with mannitol mixed liquid for use to repeatedly use for mannitol crystallization. The decolorizing reaction is carried out for 30-60 min, generally 40min, at the decolorizing temperature of 70-78 ℃.
Example 3
A method for separating mannitol mother liquor by simulated moving bed chromatography comprises the following steps:
s1, continuously introducing a mannitol mother solution and an elution phase into a simulated moving bed chromatographic system, and respectively collecting a sorbitol solution and a mannitol solution from an extracting solution extraction point and a raffinate extraction point of the simulated moving bed chromatographic system;
and S2, respectively carrying out post-treatment on the collected sorbitol solution and mannitol solution to obtain a sorbitol product and a mannitol product.
The three-stage crystallization process of mannitol generates a large amount of mannitol mother liquor, and the components comprise 74.28% of sorbitol, 14.35% of mannitol and 52.0% of solids, and the raw material composition is used as feed data of simulated moving bed chromatographic separation.
The simulated moving bed chromatographic separation device adopts styrene strong acid primary color spectrum separation resin as a stationary phase, the ion type is calcium type, the calcium type rate is higher than 95%, the particle size is 35-75 micrometers, the total exchange capacity of the resin volume is 4.5-5.5 mmol/g, and the wet apparent density is 0.84-0.89 g/ml. The method is used for separating mannitol, and has the characteristics of uniform particle size, high calcium type rate, good mechanical strength, strong pollution resistance and the like. The elution phase is degassed reverse osmosis water, and is green, environment-friendly and pollution-free. The chromatographic resin selected in this example was MonojetTM S1860。
The system is operated in sections, each step has a reference time interval, and the total time interval is 4 time intervals, namely TA, TB, TC and TD. Each time interval has an accumulated flow for program switching, and when the accumulated amount is reached in the time interval, the system performs step switching. The 4 cumulative flow values are: VA, VB, VC and VD, when the accumulated value is reached, the system is switched, and a process flow chart is shown in attached figure 1.
Step A mainly has a separation effect, and circulating water is used for pushing the band to move backwards.
Step B is divided into 2 stages, one stage is water inlet and water outlet BD (raffinate), and the other stage is water inlet and water outlet AD (extract), wherein the water replenishing also has the effect of promoting the band movement.
And the step C and the step D are feeding and discharging stages, two products are simultaneously carried out, the occupied time is shortened, and a good separation effect is generated.
In practical applications, the feeding flow rate of the mannitol mother liquor in step S1 is generally set to 3-4 m3H is 3.1 to 3.5m3More preferably in the range of/h;
the elution flow rate of the elution phase is generally set to 10.0 to 10.9m3H is 10.2 to 10.6m3More preferably in the range of/h;
the flow rate of the extract is generally set to 5.50 to 6.50m3H is 5.90 to 6.15m3More preferably in the range of/h;
the flow rate of the raffinate is generally set at 7.20 to 8.10m3H is 7.40-7.80 m3The range of the ratio of the carbon monoxide to the hydrogen is more preferable.
Subsequently, the separated product is further pretreated and refined:
(1) AD separating medium: the decolorizing temperature of the activated carbon is 70-78 ℃, the reaction time is 30-60 minutes, generally 40 minutes are selected, the activated carbon is filtered by a plate and frame filter, then the activated carbon is filtered by a cation-anion exchange resin column to adsorb metal and nonmetal impurities, and then the activated carbon is evaporated by a four-effect evaporator to obtain 70% medical grade 0270C sorbitol solution, and the 70% 0270C sorbitol solution can be continuously crystallized to be used for producing crystalline sorbitol, such as H20-H60 sorbitol.
(2) BD separation liquid: the method comprises the steps of firstly adopting three-stage membrane filtration to increase the concentration of feed liquid from 10-13% to 20-30%, then adsorbing metal and non-metal impurities through an activated carbon decoloration cation anion exchange resin column, and finally matching with mannitol mixed liquid for use to repeatedly use for mannitol crystallization. The decolorizing reaction is carried out for 30-60 min, generally 40min, at the decolorizing temperature of 70-78 ℃.
Example 4
A method for separating mannitol mother liquor by simulated moving bed chromatography comprises the following steps:
s1, continuously introducing a mannitol mother solution and an elution phase into a simulated moving bed chromatographic system, and respectively collecting a sorbitol solution and a mannitol solution from an extracting solution extraction point and a raffinate extraction point of the simulated moving bed chromatographic system;
and S2, respectively carrying out post-treatment on the collected sorbitol solution and mannitol solution to obtain a sorbitol product and a mannitol product.
The three-stage crystallization process of mannitol generates a large amount of mannitol mother liquor, and the components comprise 74.28% of sorbitol, 14.35% of mannitol and 52.0% of solids, and the raw material composition is used as feed data of simulated moving bed chromatographic separation.
The simulated moving bed chromatographic separation device adopts styrene strong acid primary color spectrum separation resin as a stationary phase, the ion type is calcium type, the calcium type rate is higher than 95%, the particle size is 35-75 micrometers, the total exchange capacity of the resin volume is 4.5-5.5 mmol/g, and the wet apparent density is 0.84-0.89 g/ml. The method is used for separating mannitol, and has the characteristics of uniform particle size, high calcium type rate, good mechanical strength, strong pollution resistance and the like. The elution phase is degassed reverse osmosis water, and is green, environment-friendly and pollution-free. The chromatographic resin selected for use in this example was Amberlite CR1310 Ca.
The system is operated in sections, each step has a reference time interval, and the total time interval is 4 time intervals, namely TA, TB, TC and TD. Each time interval has an accumulated flow for program switching, and when the accumulated amount is reached in the time interval, the system performs step switching. The 4 cumulative flow values are: VA, VB, VC and VD, when the accumulated value is reached, the system is switched, and a process flow chart is shown in attached figure 1.
Step A mainly has a separation effect, and circulating water is used for pushing the band to move backwards.
Step B is divided into 2 stages, one stage is water inlet and water outlet BD (raffinate), and the other stage is water inlet and water outlet AD (extract), wherein the water replenishing also has the effect of promoting the band movement.
And the step C and the step D are feeding and discharging stages, two products are simultaneously carried out, the occupied time is shortened, and a good separation effect is generated.
In practical applications, the feeding flow rate of the mannitol mother liquor in step S1 is generally set to 3-4 m3H is 3.1 to 3.5m3More preferably in the range of/h;
the elution flow rate of the elution phase is generally set to 10.0 to 10.9m3H is 10.2 to 10.6m3More preferably in the range of/h;
the flow rate of the extract is generally set to 5.50 to 6.50m3H is 5.90 to 6.15m3More preferably in the range of/h;
the flow rate of the raffinate is generally set at 7.20 to 8.10m3H is 7.40 to 7.80m3The range of the ratio of the carbon monoxide to the hydrogen is more preferable.
Subsequently, the separated product is further pretreated and refined:
(1) AD separating medium: the decolorizing temperature of the activated carbon is 70-78 ℃, the reaction time is 30-60 minutes, generally 40 minutes are selected, the activated carbon is subjected to plate-frame filter pressing, then the activated carbon is subjected to adsorption of metal and nonmetal impurities by a cation-anion exchange resin column, and then the activated carbon is evaporated into 70% pharmaceutical grade 0270C sorbitol solution by a four-effect evaporator, and the 70% 0270C sorbitol solution can also be continuously crystallized to be used for producing crystalline sorbitol, such as H20-H60 sorbitol.
(2) BD separation liquid: the method comprises the steps of firstly adopting three-stage membrane filtration to increase the concentration of feed liquid from 10-13% to 20-30%, then adsorbing metal and non-metal impurities through an activated carbon decoloration cation anion exchange resin column, and finally matching with mannitol mixed liquid for use to repeatedly use for mannitol crystallization. The decolorizing reaction is carried out for 30-60 min, generally 40min, at the decolorizing temperature of 70-78 ℃.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for recovering sorbitol and mannitol from mannitol mother liquor is characterized by comprising a step of separating and recovering sorbitol and mannitol by a simulated moving bed chromatography system,
wherein, the stationary phase adopted by the simulated moving bed chromatographic system is strong acid styrene cation exchange resin, and the ionic type is preferably Ca+And (4) molding.
2. The method of claim 1, comprising the steps of:
s1, continuously introducing a mannitol mother solution and an elution phase into a simulated moving bed chromatographic system, and respectively collecting a sorbitol solution and a mannitol solution from an extracting solution extraction point and a raffinate extraction point of the simulated moving bed chromatographic system;
and S2, respectively carrying out post-treatment on the collected sorbitol solution and mannitol solution to obtain a sorbitol product and a mannitol product.
3. The method according to claim 2, wherein the elution phase in step S1 is water, preferably deionized water, purified water or degassed reverse osmosis water;
the feed-liquid ratio of the mannitol mother liquor to the elution phase is preferably (2-3): 1, and more preferably (2.5-2.7): 1.
4. The method according to claim 2, wherein the feeding flow rate of the mannitol mother liquor in step S1 is 3-4 m3Preferably 3.1 to 3.5 m/h3/h；
The elution flow rate of the elution phase in the step S1 is preferably 10.0-10.9 m3More preferably 10.2 to 10.6 m/h3/h；
The flow rate of the extracting solution in the step S1 is preferably 5.50-6.50 m3More preferably 5.90 to 6.15 m/h3/h；
The flow rate of the raffinate in the step S1 is preferably 7.20-8.10 m3More preferably 7.40 to 7.80 m/h3/h。
5. The method of claim 2, wherein the sorbitol solution is post-treated in step S2 by decolorizing, filtering, ion exchange chromatography, and concentrating to obtain sorbitol product.
6. The method according to claim 4, wherein the decolorization treatment is activated carbon decolorization, preferably a decolorization reaction at 70-78 ℃ for 30-60 min, and more preferably a decolorization reaction at 70-78 ℃ for 40 min;
the filtration is preferably filter pressing, and more preferably plate-and-frame filter pressing;
the ion exchange chromatography is preferably to adsorb metal and nonmetal impurities through a cation and anion exchange resin column;
the concentration is preferably evaporated via a four-effect evaporator.
7. The method of claim 2, wherein the post-treatment of the mannitol solution in step S2 comprises filtration, concentration, decolorization, and ion exchange chromatography to obtain mannitol product.
8. The method according to claim 6, wherein the filtering and concentrating method is three-stage membrane filtration, and the decolorizing treatment is activated carbon decolorizing, preferably decolorizing reaction at 70-78 ℃ for 30-60 min, and more preferably decolorizing reaction at 70-78 ℃ for 40 min.
The ion exchange chromatography is preferably performed by adsorption of metallic and non-metallic impurities through a cation and anion exchange resin column.
9. The method according to claim 1, wherein the particle size of the strong-acid styrene cation exchange resin is 35-75 micrometers;
the volume total exchange capacity of the strong-acid styrene cation exchange resin is preferably 4.5-5.5 mmol/g;
the wet apparent density of the strong-acid styrene cation exchange resin is preferably 0.84-0.89 g/mL.
10. The method of claim 1, wherein the simulated moving bed chromatography system comprises 4-32 identical chromatography columns in series.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466795A (en) * | 1992-07-22 | 1995-11-14 | Roquette Freres | Process for the manufacture of mannitol |
| EP1176131A1 (en) * | 2000-07-24 | 2002-01-30 | DHW Deutsche Hydrierwerke GmbH Rodleben | Method of preparation of sorbitols from standard-glucose |
| CN1528728A (en) * | 2003-09-28 | 2004-09-15 | 南宁市化工研究设计院 | High-yield manna sugar preparation process |
| CN1721543A (en) * | 2005-06-09 | 2006-01-18 | 青岛明月海藻集团有限公司 | Novel process for producing mannitol |
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2021
- 2021-12-28 CN CN202111631875.8A patent/CN114436768A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466795A (en) * | 1992-07-22 | 1995-11-14 | Roquette Freres | Process for the manufacture of mannitol |
| EP1176131A1 (en) * | 2000-07-24 | 2002-01-30 | DHW Deutsche Hydrierwerke GmbH Rodleben | Method of preparation of sorbitols from standard-glucose |
| CN1528728A (en) * | 2003-09-28 | 2004-09-15 | 南宁市化工研究设计院 | High-yield manna sugar preparation process |
| CN1721543A (en) * | 2005-06-09 | 2006-01-18 | 青岛明月海藻集团有限公司 | Novel process for producing mannitol |
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