CN104725190A - Method for using metal-organic skeleton for adsorption and separating of polyol in aqueous solution - Google Patents
Method for using metal-organic skeleton for adsorption and separating of polyol in aqueous solution Download PDFInfo
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- CN104725190A CN104725190A CN201310704168.6A CN201310704168A CN104725190A CN 104725190 A CN104725190 A CN 104725190A CN 201310704168 A CN201310704168 A CN 201310704168A CN 104725190 A CN104725190 A CN 104725190A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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- 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
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Abstract
A method for using a metal-organic skeleton for adsorption and separating of a polyol in an aqueous solution is as follows: a metal-organic skeleton material is used as an adsorbent, the polyol in the aqueous solution can be highly selectively adsorbed in the porous material, after the adsorption, anhydrous ethanol is used for desorption, and ethanol in the desorption liquid is removed to obtain the single polyol. The method has the advantages of simple process and high separation efficiency, solves the bottleneck problem in the process of the production of the polyol, and has good industrial application prospect.
Description
Technical field:
The present invention relates to separation technology field, be specifically related to a kind of method adopting metal-organic framework materials fractionation by adsorption polyvalent alcohol from the aqueous solution.
Background technology:
Polyvalent alcohol is widely used in multiple fields such as chemical industry, food, fuel and aerospace.As the raw material producing terylene and explosive is not only by ethylene glycol, be also widely used in food and medicine industry; The raw material preparing explosive is not only by glycerine, also applies a lot of in the industry such as plastics, makeup.At present, the effect as the polyvalent alcohol of Energy Platform of new generation highlights more.The production method of current polyvalent alcohol has chemical synthesis and microbe fermentation method, and relative to chemical synthesis, fermentable is produced polyvalent alcohol and had the advantages such as raw material is renewable, easy and simple to handle, reaction conditions is gentle, by product is less, environmental pollution is little.Along with the scarcity day by day of petroleum resources, the route of renewable resources fermentative production polyvalent alcohol is utilized more and more to receive publicity.When utilizing fermentable to produce polyvalent alcohol, the complicacy due to fermented liquid system makes product separation purifying cost account for more than 50% of total production cost, becomes the bottleneck problem of scale operation polyvalent alcohol.The content of usual polyvalent alcohol in biomass ferment liquid is only 30-110g/L, and the material that polyvalent alcohol is all high boiling point simultaneously, wetting ability is strong, therefore, being separated from water by polyvalent alcohol is a difficult task.Traditional rectification method energy consumption is very large, and solvent extration needs to consume a large amount of organic solvents and the problem bringing later separation, and in contrast, adsorption method of separation is the operational path of efficient a, low consumption, environmental protection.
Absorption is a kind of Solid phase extraction separation technology of less energy-consumption.Because the molecule of solid surface or atom have remaining surface energy because of discontinuity equalization during adsorption.When Cucumber colliding solid surface time, receive the attraction of these unbalanced forces and be detained on a solid surface, make by binding molecule adsorbent surface concentration higher than solution bulk mutually in concentration.For the fractionation by adsorption of polyvalent alcohol, the sorbent material reported at present has the silica gel of modification, XAD series plastics and molecular sieve.Wherein, comparatively special by the absorption principle of the silica gel of phenyl-boron dihydroxide modification, the boron hydroxyl on sorbent material can with the hydroxyl generation chemical reaction of dibasic alcohol, this stronger chemical action makes sorbent material have good absorption property to polyvalent alcohol just.Adsorptive capacity for C2-C4 glycols is as follows: ethylene glycol: 0.062g/g, 1,2-PD: 0.076g/g, 1,2-butyleneglycol: 0.090g/g.For the absorption of 1,3-PD, XAD series plastics and molecular sieve show good absorption property, as: XAD-7 resin absorption amount reaches 0.240g/g, and XAD-16 resin absorption amount reaches 0.160g/g, and FX-II zeolite adsorption amount reaches 0.121g/g.Although these porous materials show certain adsorption separation performance for polyvalent alcohol, because the modulation that is difficult to of its pore passage structure and surface properties makes to improve adsorptive capacity further and is restricted.
Metallo-organic framework has become a focus in investigation of materials field, and it is by metal ion or ion cluster and forms the crystalline material with periodically infinite network structure, also known as Porous coordination polymer containing the organic ligand of oxygen or nitrogen.More classical and study more metal-organic framework materials and have MOF-5, HKUST-1 and MIL series.Zeolite imidazole ester frame structure material, being called for short (ZIFs) is with the kind skeleton structure of zeolite material that organic imidazate is formed for part in MOFs material.The divalent-metal ions such as Zn/Co replace the Silicified breccias in traditional zeolite molecular sieve, miaow or miaow derivative replace bridging oxygen, be connected by the atom N on imidazole ring and form, the zeolite structured ZIFs of making of this kind has stronger hydrothermal stability compared with the MOFs material of other type.
With conventional inorganic zeolite facies ratio, metallic organic framework is by introducing different organic ligands and carrying out the design of functional group to organic ligand and modify the structure of adjusting hole, size and surface properties.Yaghi study group has synthesized the MOFs of a series of different pore size by the phenyl ring number increased in organic ligand, expands to mesoporous by the aperture of MOF from micropore, thus can be applicable to medicine and biological aspect.In addition, also by the physico-chemical property of rear synthetic modification modulation MOFs skeleton, new functional group can be introduced in skeleton.Such as, Yaghi study group will contain the ZIF-90 of aldehyde radical through NaBH
4reduce or react with thanomin the ZIF-92 transforming and obtain hydroxyl ZIF-91 or be with imido grpup.The performance of these excellences makes metallic organic framework in a lot of field as atmosphere storage just, and be separated, catalysis etc. have very widespread use.Long seminar finds that Fe-MOF-74 has good separation performance to light hydrocarbons, and it is different with alkane absorption property that adsorption isothermal line shows the alkene of this kind of material to different C chain, can realize adsorption selection.The breakthrough curve obtained as can be seen from theoretical modeling, can realize the separation one by one of light hydrocarbons by appropriate design adsorption bed.
Summary of the invention:
The object of the invention is for existing in polyvalent alcohol sepn process that energy consumption is high, high in cost of production problem, a kind of method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution is provided, the method utilizes the fractionation by adsorption effect of metallic organic framework, polyvalent alcohol in fractionate aqueous solutions, reduces separation costs.
The invention provides a kind of method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution, the concrete steps of the method are as follows: (1) utilizes static adsorptive method or dynamic adsorption method to adsorb polyvalent alcohol, obtains the mixing solutions of polyvalent alcohol and ethanol;
The step of static adsorptive method is as follows: joined in polyatomic alcohol water solution by metal-organic framework materials and adsorb, filtering separation, and resolve with dehydrated alcohol after absorption, centrifugation after resolving, obtains the mixing solutions of polyvalent alcohol and ethanol;
The step of dynamic adsorption method is as follows: loaded by metal-organic framework materials in adsorption column, polyatomic alcohol water solution is adsorbed by adsorption column, then with the polyatomic alcohol water solution do not adsorbed in deionized water rinsing adsorption column, carry out wash-out with dehydrated alcohol again, collect the mixing solutions that elutriant is polyvalent alcohol and ethanol.
(2) polyvalent alcohol obtained above-mentioned steps and the mixing solutions of ethanol distill, and obtain single polyvalent alcohol.
The method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution provided by the invention, described metal-organic framework materials is CAU-10, UiO-66, MIL-47, MIL-53 (Al), MIL-53 (Al)-NH
2, MIL-53 (Cr), MIL-53 (Cr)-NH
2, MIL-100, MIL-101, MIL-101-NH
2, the one in MIL-103, ZIF-7, ZIF-8, ZIF-25, ZIF-68, ZIF-69, ZIF-70, ZIF-71, ZIF-78, ZIF-90, ZIF-91, ZIF-93, ZIF-96, ZIF-97, ZIF-108; The granular size of metal-organic framework materials there is no too large requirement, but considers adsorption effect, is preferably 40nm-1 μm.
Described polyvalent alcohol is the one in ethylene glycol, 1,2-PD, 1,3-PD, glycerol, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butanediol.The massfraction of described polyatomic alcohol water solution is 0.01-10wt.%.
The method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution provided by the invention, the adsorption conditions in described static adsorptive method is: adsorption temp is 25-50 DEG C, and adsorption time is 1min-24h.
The method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution provided by the invention, the adsorption temp in described dynamic adsorption method is 25 DEG C.
Metal-organic framework materials is put in polyatomic alcohol water solution by the inventive method, can complete the adsorption process of highly selective at normal temperatures.The present invention uses ethanol to carry out desorption, and the reclaiming process of sorbent material is simple, and cost recovery is low.The present invention has the advantages such as environmental friendliness, simple to operate, sorbent material recoverable.
Accompanying drawing illustrates:
Accompanying drawing 1 is the X-ray diffractogram of embodiment 1 metal-organic framework materials ZIF-93 used;
Accompanying drawing 2 is the scanning electron microscope diagram of embodiment 1 metal-organic framework materials ZIF-93 used;
Accompanying drawing 3 is the X-ray diffractogram of embodiment 2 metal-organic framework materials ZIF-8 used;
Accompanying drawing 4 is the scanning electron microscope diagram of embodiment 2 metal-organic framework materials ZIF-8 used;
Accompanying drawing 5 is the breakthrough curve of 1,3-PD on metal-organic framework materials ZIF-8 in embodiment 2
Accompanying drawing 6 is the wash-out of 1,3-PD on metal-organic framework materials ZIF-8 in embodiment 2
Accompanying drawing 7 is the X-ray diffractogram of embodiment 2 metal-organic framework materials ZIF-90 used;
Accompanying drawing 8 is the scanning electron microscope diagram of embodiment 2 metal-organic framework materials ZIF-90 used;
Accompanying drawing 9 is the breakthrough curve of ethylene glycol on metal-organic framework materials ZIF-90 in embodiment 2
Accompanying drawing 10 is the wash-out of ethylene glycol on metal-organic framework materials ZIF-90 in embodiment 2
Embodiment:
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1 adopts metal-organic framework materials ZIF-93 to adsorb 1,3 butylene glycol static aqueous solution
Step 1: obtain clear liquid by after 1,3 butylene glycol filtering fermentation liquor removing thalline, regulate pH with KOH, make its pH be 7.0.
Step 2: be 1 of 5wt.% by massfraction, 3-butyleneglycol aqueous solution 2ml joins in the vial of 5ml and adsorbs, vial is its X-ray diffraction phenogram built with 0.2g metal-organic framework materials ZIF-93(Fig. 1, can find out that from electron scanning micrograph (Fig. 2) average particulate diameter of ZIF-93 is 50nm), 25 DEG C of stirrings, 24h is centrifugal, in liquid chromatogram measuring supernatant liquid 1 in absorption, the concentration of 3-butyleneglycol, adsorptive capacity reaches 0.15g/g ZIF-93.
Step 3: add 1ml ethanol, stirring at room temperature 24h in step 2 gained precipitation, centrifugation obtains supernatant liquid, and distillation obtains 1,3 butylene glycol, and the rate of recovery is 90%.
Embodiment 2 adopts metal-organic framework materials ZIF-8 to 1,3-PD aqueous solution dynamic adsorption
Step 1: obtain clear liquid by after 1,3-PD filtering fermentation liquor removing thalline, regulate pH with KOH, make its pH be 7.0.
Step 2: be its X-ray diffraction phenogram by 0.20g metal-organic framework materials ZIF-8(Fig. 3, can find out that from electron scanning micrograph (Fig. 4) average particulate diameter of ZIF-93 is 40nm) load
gc column tube, clear liquid step 1 processed with 0.05ml/min flow velocity, by gc column tube, samples in exit at regular intervals, to use in liquid-phase chromatographic analysis institute sample thief 1, the content of ammediol, until the content going out oral fluid 1,3-PD reaches concentration of raw material.Make out the content graph of a relation over time of 1,3-PD in oral fluid, i.e. the breakthrough curve of 1,3-PD on ZIF-8 (as Fig. 5).
Step 3: with do not adsorb in gc column tube in the deionized water rinsing step 2 of 2 times of column volumes 1, after ammediol fermented liquid, wash-out is carried out again with dehydrated alcohol, elution flow rate is 0.05ml/min, at regular intervals in exit sampling, to use in liquid-phase chromatographic analysis institute sample thief 1, the content of ammediol, until the content of exit 1,3-PD is close to 0, elution curve as shown in Figure 6.The elutriant that collection obtains carries out distillation and obtains 1,3-PD, and the rate of recovery of 1,3-PD is 92.1%.
Embodiment 3 adopts metal-organic framework materials ZIF-90 to aqueous glycol solution dynamic adsorption
Step 1: obtain clear liquid by after ethylene glycol filtering fermentation liquor removing thalline, regulate pH with KOH, make its pH be 7.0.
Step 2: be its X-ray diffraction phenogram by 0.20g metal-organic framework materials ZIF-90(Fig. 7, can find out that from electron scanning micrograph (Fig. 8) average particulate diameter of ZIF-93 is 100nm) load
gc column tube, gc column tube is passed through with the clear liquid that step 1 processed by 0.05ml/min flow velocity, at regular intervals in exit sampling, use the content of ethylene glycol in liquid-phase chromatographic analysis institute sample thief, until the content going out oral fluid ethylene glycol reaches concentration of raw material.Make out the content graph of a relation over time of 1,3-PD in oral fluid, i.e. the breakthrough curve of ethylene glycol on ZIF-90, as Fig. 9.
Step 3: after the ethylene glycol fermented liquid do not adsorbed in gc column tube in the deionized water rinsing step 2 of 2 times of column volumes, wash-out is carried out again with dehydrated alcohol, elution flow rate is 0.05ml/min, sample in exit at regular intervals, use the content of ethylene glycol in liquid-phase chromatographic analysis institute sample thief, until the content of exit ethylene glycol is close to 0, elution curve as shown in Figure 10.The elutriant that collection obtains carries out distillation and obtains ethylene glycol, and the rate of recovery of ethylene glycol is 93.5%.
Claims (6)
1. utilize a method for polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution, it is characterized in that: the concrete steps of the method are as follows:
(1) utilize static adsorptive method or dynamic adsorption method to adsorb polyvalent alcohol, obtain the mixing solutions of polyvalent alcohol and ethanol;
The step of static adsorptive method is as follows: joined in polyatomic alcohol water solution by metal-organic framework materials and adsorb, filtering separation, and resolve with dehydrated alcohol after absorption, centrifugation after resolving, obtains the mixing solutions of polyvalent alcohol and ethanol;
The step of dynamic adsorption method is as follows: loaded by metal-organic framework materials in adsorption column, polyatomic alcohol water solution is adsorbed by adsorption column, then with the polyatomic alcohol water solution do not adsorbed in deionized water rinsing adsorption column, carry out wash-out with dehydrated alcohol again, collect the mixing solutions that elutriant is polyvalent alcohol and ethanol.
(2) polyvalent alcohol obtained above-mentioned steps and the mixing solutions of ethanol distill, and obtain single polyvalent alcohol.
2. according to the method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution described in claim 1, it is characterized in that: described metal-organic framework materials is CAU-10, UiO-66, MIL-47, MIL-53 (Al), MIL-53 (Al)-NH2, MIL-53 (Cr), MIL-53 (Cr)-NH2, MIL-100, MIL-101, MIL-101-NH2, MIL-103, ZIF-7, ZIF-8, ZIF-25, ZIF-68, ZIF-69, ZIF-70, ZIF-71, ZIF-78, ZIF-90, ZIF-91, ZIF-93, one in ZIF-96, ZIF-97, ZIF-108.
3. according to the method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution described in claim 1, it is characterized in that: described polyvalent alcohol is ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerol, 1,2-butyleneglycol, 1, one in 3-butyleneglycol, BDO, 2,3-butanediol.
4. according to the method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution described in claim 1, it is characterized in that: the massfraction of described polyatomic alcohol water solution is 0.01-10wt.%.
5. according to the method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution described in claim 1, it is characterized in that: the adsorption conditions in described static adsorptive method is: adsorption temp is 25-50 DEG C, adsorption time is 1min-24h.
6. according to the method utilizing polyvalent alcohol in the metal-organic framework fractionation by adsorption aqueous solution described in claim 1, it is characterized in that: the adsorption temp in described dynamic adsorption method is 25 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106110908A (en) * | 2016-07-05 | 2016-11-16 | 浙江赛特膜技术有限公司 | The preparation method of aromatic polyamides hydridization NF membrane |
| CN106589398A (en) * | 2016-12-06 | 2017-04-26 | 首都师范大学 | Zirconium organic frame material and preparation method and application thereof |
| CN110780001A (en) * | 2019-11-05 | 2020-02-11 | 兰州东立龙信息技术有限公司 | Gas chromatographic column and preparation method thereof |
| CN114015063A (en) * | 2021-10-22 | 2022-02-08 | 太原理工大学 | Nitro-ligand-doped zeolitic imidazolate framework material ZIF-71-clnImxPreparation and use of |
| CN114288713A (en) * | 2021-12-07 | 2022-04-08 | 宁夏大学 | Oil-water separation membrane based on metal organic framework material switchable surface wettability and preparation method thereof |
| CN115508475A (en) * | 2022-11-01 | 2022-12-23 | 未名环境分子诊断(广东)有限公司 | Method for detecting content of diphenoxylate in sewage |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874524A (en) * | 1988-03-30 | 1989-10-17 | The Curators Of The University Of Missouri | Separation of adsorbed components by variable temperature desorption |
| CN101274876A (en) * | 2008-05-16 | 2008-10-01 | 南京工业大学 | Method for adsorptive separating 2, 3-butanediol from fermentation liquor by using hydrophobic zeolite |
| WO2010012660A1 (en) * | 2008-07-31 | 2010-02-04 | Shell Internationale Research Maatschappij B.V. | Process for producing alcohol |
| CN102389686A (en) * | 2011-09-22 | 2012-03-28 | 中国石油大学(北京) | Separating method for CO2-containing mixed gas |
| WO2012164395A1 (en) * | 2011-05-31 | 2012-12-06 | King Abdullah University Of Science And Technology | Zeolitic imidazolate framework membranes and methods of making and using same for separation of c2- and c3+ hydrocarbons and separation of propylene and propane mixtures |
-
2013
- 2013-12-18 CN CN201310704168.6A patent/CN104725190A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874524A (en) * | 1988-03-30 | 1989-10-17 | The Curators Of The University Of Missouri | Separation of adsorbed components by variable temperature desorption |
| CN101274876A (en) * | 2008-05-16 | 2008-10-01 | 南京工业大学 | Method for adsorptive separating 2, 3-butanediol from fermentation liquor by using hydrophobic zeolite |
| WO2010012660A1 (en) * | 2008-07-31 | 2010-02-04 | Shell Internationale Research Maatschappij B.V. | Process for producing alcohol |
| WO2012164395A1 (en) * | 2011-05-31 | 2012-12-06 | King Abdullah University Of Science And Technology | Zeolitic imidazolate framework membranes and methods of making and using same for separation of c2- and c3+ hydrocarbons and separation of propylene and propane mixtures |
| CN102389686A (en) * | 2011-09-22 | 2012-03-28 | 中国石油大学(北京) | Separating method for CO2-containing mixed gas |
Non-Patent Citations (1)
| Title |
|---|
| STUART L. JAMES: "Metal-organic frameworks", 《CHEM. SOC. REV.》 * |
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| CN106110908A (en) * | 2016-07-05 | 2016-11-16 | 浙江赛特膜技术有限公司 | The preparation method of aromatic polyamides hydridization NF membrane |
| CN106589398A (en) * | 2016-12-06 | 2017-04-26 | 首都师范大学 | Zirconium organic frame material and preparation method and application thereof |
| CN110780001A (en) * | 2019-11-05 | 2020-02-11 | 兰州东立龙信息技术有限公司 | Gas chromatographic column and preparation method thereof |
| CN114015063A (en) * | 2021-10-22 | 2022-02-08 | 太原理工大学 | Nitro-ligand-doped zeolitic imidazolate framework material ZIF-71-clnImxPreparation and use of |
| CN114015063B (en) * | 2021-10-22 | 2023-01-10 | 太原理工大学 | Nitro-ligand-doped zeolitic imidazolate framework material ZIF-71-clnIm x Preparation and use of |
| CN114288713A (en) * | 2021-12-07 | 2022-04-08 | 宁夏大学 | Oil-water separation membrane based on metal organic framework material switchable surface wettability and preparation method thereof |
| CN114288713B (en) * | 2021-12-07 | 2023-04-07 | 宁夏大学 | Oil-water separation membrane based on metal organic framework material switchable surface wettability and preparation method thereof |
| CN115508475A (en) * | 2022-11-01 | 2022-12-23 | 未名环境分子诊断(广东)有限公司 | Method for detecting content of diphenoxylate in sewage |
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