CN117417394A - Method for recycling fructose from 5-hydroxymethylfurfural wastewater - Google Patents
Method for recycling fructose from 5-hydroxymethylfurfural wastewater Download PDFInfo
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- CN117417394A CN117417394A CN202311429396.7A CN202311429396A CN117417394A CN 117417394 A CN117417394 A CN 117417394A CN 202311429396 A CN202311429396 A CN 202311429396A CN 117417394 A CN117417394 A CN 117417394A
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- fructose
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- 239000005715 Fructose Substances 0.000 title claims abstract description 47
- 229930091371 Fructose Natural products 0.000 title claims abstract description 47
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 47
- 239000002351 wastewater Substances 0.000 title claims abstract description 30
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 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 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 235000011010 calcium phosphates Nutrition 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229960005069 calcium Drugs 0.000 claims 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 235000010216 calcium carbonate Nutrition 0.000 claims 1
- 229960002713 calcium chloride Drugs 0.000 claims 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims 1
- 229960001714 calcium phosphate Drugs 0.000 claims 1
- 229940095672 calcium sulfate Drugs 0.000 claims 1
- 235000019700 dicalcium phosphate Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 239000000706 filtrate Substances 0.000 abstract description 8
- 239000002028 Biomass Substances 0.000 abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 235000001465 calcium Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention belongs to the technical field of biomass wastewater utilization, and particularly relates to a method for recycling fructose from 5-Hydroxymethylfurfural (HMF) wastewater. In order to solve the problem of the current recovery of HMF waste water fructose: the invention mixes the waste water and calcium source in the solvent, the sediment obtained by filtering is washed by weak acid, the filtrate is concentrated and crystallized after passing through the ion exchange column, and the fructose with high purity and high yield is obtained. The used calcium source is common inorganic salt, is green and pollution-free, can utilize various different solvents to regulate and control the reaction, improves the selectivity of fructose recovery, and can realize recycling by further processing, separating and purifying the solvent and the calcium source.
Description
Technical Field
The invention relates to the technical field of biomass wastewater utilization, in particular to a method for recycling fructose from 5-Hydroxymethylfurfural (HMF) wastewater.
Background
As a natural food additive, fructose has the advantages of good taste, high sweetness and low calorific value, and is widely applied to important fields such as food, medicine and the like. Meanwhile, due to the specificity of the chemical structure, fructose is also an important raw material for producing 5-Hydroxymethylfurfural (HMF), and HMF is an important platform compound for producing alternative biomass chemical products, so that the method has wide application prospect.
The preparation system of the HMF at the present stage is mainly divided into a water phase system and an organic phase system, but the problems of incomplete reaction, low product purity, difficult separation and the like exist at present, so that a certain amount of fructose which is not completely reacted exists in the waste water of the HMF. The existing recovery method of fructose in wastewater is mainly characterized in that inorganic salt represented by lime milk is added for calcification recovery, the method needs low-temperature operation and strict control of solution pH, the reaction condition is harsh, the fructose yield is low, and the quality of the prepared fructose is difficult to reach the standard of biochemical reagents and is difficult to realize on a large scale.
Therefore, if an industrialized fructose recovery method with controllable temperature, mild reaction conditions, simple and convenient operation and easy grasp can be developed, a new solution is developed for the efficient utilization of HMF wastewater.
Disclosure of Invention
In order to solve the problem of the current recovery of HMF waste water fructose: the invention provides a method for recycling fructose from 5-Hydroxymethylfurfural (HMF) wastewater, which is characterized in that wastewater and a calcium source are mixed in a solvent for reaction, and the fructose is recycled through ion replacement and evaporation concentration.
In order to achieve the purpose of the invention, the technical scheme of the invention is as follows:
in a first aspect, the invention provides a method for recycling fructose from 5-Hydroxymethylfurfural (HMF) wastewater, which comprises the steps of mixing wastewater and calcium sources in a solvent, washing a filtered precipitate by weak acid, and concentrating and crystallizing the filtrate after passing through an ion exchange column to obtain high-purity and high-yield fructose. The method comprises the following steps:
step 1, mixing the wastewater and a calcium source to obtain a mixed solution.
And 2, adding a solvent into the mixed solution obtained in the step 1, and washing the obtained precipitate by using weak acid.
And 3, passing the washing liquid obtained in the step 2 through an ion exchange column, and evaporating and concentrating the obtained washing liquid and the exchange liquid to obtain fructose.
The invention mixes the waste water and the calcium source in the solvent, the sediment obtained by filtering is washed by weak acid, and the filtrate is concentrated and crystallized after passing through the ion exchange column, thus obtaining the fructose with high purity and high yield. The used calcium source is common inorganic salt, is green and pollution-free, can utilize various different solvents to regulate and control the reaction, improves the selectivity of fructose recovery, and can realize recycling by further processing, separating and purifying the solvent and the calcium source.
Further, the calcium source in the step 1 is one of calcium chloride, calcium phosphate, calcium sulfate, calcium acetate, calcium hydrophosphate, calcium biphosphate and calcium carbonate or a mixture of the calcium phosphate, the calcium biphosphate and the calcium carbonate.
Further, the solvent in the step 2 is one or more mixed solvents of methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, glycerol, butanediol, ethylenediamine, ethanolamine, diethyl ether, acetylacetone, N-dimethylformamide and N, N-dimethylacetamide according to any proportion.
Preferably, the molar ratio of the calcium ions in the wastewater and the calcium source in the step 1 is as follows: 1:0.5-20.
Preferably, the reaction temperature in the step 1 is 10-100 ℃ and the reaction time is 5 min-24 h.
Preferably, the weak acid in the step 2 specifically includes at least one of carbonic acid, acetic acid, silicic acid, nitrous acid, hydrogen sulfate, hypochlorous acid, sulfurous acid, and phosphoric acid.
Further preferably, the pH of the mixed solution in the step 2 is 4-7.
Further, the specific steps of ion exchange and recovery of crystalline fructose in the step 3 are as follows:
(1) The filtrate obtained in step 2 is exchanged by a 732 type cation exchange resin and/or a 704 type weak base resin.
(2) Collecting the washing liquid and the exchange liquid, concentrating by a thin film evaporator until no water is distilled out, adding equal amount of methanol for dissolution, decoloring and filtering by active carbon.
(3) Adding a small amount of fructose seed crystal, stirring and crystallizing.
The raw materials or the reagents involved in the invention are all common commercial products, and the related operations are all routine operations in the field unless specified.
The above-mentioned preferable conditions can be combined with each other to obtain a specific embodiment on the basis of common knowledge in the art.
Compared with the prior art, the invention has the following advantages:
(1) Improves the yield and the utilization rate of the fructose.
(2) Can separate and purify fructose from wastewater to obtain fructose products with high yield.
(3) The reaction condition is simple and the operation is controllable.
Drawings
FIG. 1 is a chromatogram of fructose content prior to treatment in example 1;
FIG. 2 is a chromatogram of fructose content after treatment in example 1.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be made. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the invention.
Preferred embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The percentages appearing in the examples below are percentages by mass unless otherwise indicated.
In the embodiment of the invention, a Waters 2695 liquid chromatograph is adopted for fructose content detection.
Example 1
Preparing a fructose aqueous solution with the mass fraction of 70%, adding an appropriate amount of acid catalyst, taking acetone as an organic solvent, reacting for 1h at 130 ℃ in a multifunctional reaction kettle to obtain a primary reaction solution, removing the organic solvent by rotary evaporation, using water phase wastewater containing fructose obtained after extraction by ethyl acetate, weighing 100g of wastewater to be treated containing fructose, and adding 11.95g of CaCl 2 Stirring and mixing to obtain fructose-CaCl 2 After the double salt is reacted for 3 hours at 25 ℃, adding 100g of excessive ethanol and solution for mixing, fully reacting, standing and filtering to obtain double salt precipitate; dissolving the precipitate in 500mL of 10% by mass of carbonic acid aqueous solution, wherein the pH of the mixed solution is 5.5, filtering, exchanging the filtrate by 732 type cation exchange resin, collecting washing liquid and exchange liquid, concentrating by a thin film evaporator until no water is distilled out, adding equal amount of methanol for dissolving, adding 1% of active carbon for decoloring and filtering, adding a small amount of fructose crystal seeds for stirring and crystallizing, and obtaining crude fructose with the yield of 52.8%.
Example 1 the chromatograms of fructose content before and after treatment are shown in figures 1 and 2.
Example 2
The source of waste water is the same as that of example 1, 100g of waste water to be treated with fructose content of 22.17% is weighed in a 500mL beaker, calcium acetate is added according to the molar ratio of fructose to calcium ions of 1:1, the reaction is carried out for 1h at 25 ℃, 100g of isopropanol is gradually added after the reaction is completed, the reaction is carried out for layering fully, the double salt precipitate obtained by filtration is dissolved in the mixed solution of acetic acid, the pH value of the mixed solution is 5.1, twice distilled water is utilized to carry out ion exchange on the filtrate obtained by filtration through 704 weak base resin, washing liquid and exchange liquid are collected, evaporated and concentrated, after 1% active carbon is decolorized, a small amount of fructose crystal seeds are added for crystallization, and the final crude fructose is obtained, and the yield is 40.54%.
Example 3
The waste water source was the same as in example 1, and waste water, calcium phosphate and sodium chloride were weighed according to a molar ratio of fructose to calcium ions in the waste water of 1:3, with the mass of 100g, 50.12g and 5.9g, respectively. The reaction temperature is between 10 and 20 ℃ and the reaction time is 2 hours. After the reaction is finished, adding a mixed solution of methanol and glycol, filtering after the full reaction is finished, dissolving the obtained precipitate in a mixed solution of hypochlorous acid and acetic acid, wherein the pH value of the mixed solution is 5.7, exchanging the filtrate by 732 type cation exchange resin and 704 type weak base resin, collecting washing liquid and exchange liquid, concentrating by a thin film evaporator until no water is evaporated, adding equal amount of methanol for dissolving, decoloring and filtering by active carbon, and crystallizing the filtrate to obtain crude fructose with the yield of 48.99 percent.
Claims (8)
1. The method for recycling the fructose from the 5-hydroxymethylfurfural wastewater is characterized by comprising the following steps of:
step 1: mixing waste water and a calcium source in the production of the 5-hydroxymethylfurfural containing fructose for reaction to obtain a mixed solution;
step 2: adding a solvent into the mixed solution obtained in the step 1, and dissolving the precipitate obtained after the full reaction by weak acid to obtain a washing solution;
step 3: and (3) carrying out ion exchange and recovery crystallization on the washing liquid obtained in the step (2) to obtain fructose.
2. The method according to claim 1, wherein in step 1, the calcium source is one of calcium chloride, calcium phosphate, calcium sulfate, calcium acetate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium carbonate or a mixture with sodium chloride and potassium chloride.
3. The method according to claim 1, wherein in the step 1, the molar ratio of fructose in the wastewater to calcium ions in the calcium source is 1:0.5 to 20.
4. The method according to claim 1, wherein in the step 1, the temperature of the mixing reaction is 10 to 100 ℃, and the time of the mixing reaction is 5min to 24h.
5. The method according to claim 1, wherein in the step 2, the solvent is one or more mixed solvents selected from methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, glycerol, butanediol, ethylenediamine, ethanolamine, diethyl ether, acetylacetone, N-dimethylformamide and N, N-dimethylacetamide according to any proportion.
6. The method according to claim 1, wherein in step 2, the weak acid is at least one of carbonic acid, acetic acid, silicic acid, nitrous acid, hydrogen sulfuric acid, hypochlorous acid, sulfurous acid, and phosphoric acid.
7. The method according to claim 1, wherein in step 2, the pH of the mixture is 4-7.
8. The method according to claim 1, wherein in step 3, the ion exchange and recovery crystallization, in particular, comprises:
(1) Exchanging the washing liquid obtained in the step 2 by 732 type cation exchange resin and/or 704 type weak base resin;
(2) Collecting washing liquid and exchange liquid, concentrating by a thin film evaporator until no water is distilled out, adding methanol for dissolving, decolorizing with active carbon, and filtering;
(3) Adding fructose seed crystal, stirring and crystallizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311429396.7A CN117417394A (en) | 2023-10-31 | 2023-10-31 | Method for recycling fructose from 5-hydroxymethylfurfural wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311429396.7A CN117417394A (en) | 2023-10-31 | 2023-10-31 | Method for recycling fructose from 5-hydroxymethylfurfural wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117417394A true CN117417394A (en) | 2024-01-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311429396.7A Pending CN117417394A (en) | 2023-10-31 | 2023-10-31 | Method for recycling fructose from 5-hydroxymethylfurfural wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117417394A (en) |
-
2023
- 2023-10-31 CN CN202311429396.7A patent/CN117417394A/en active Pending
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