WO2019101160A1 - 一种含有呋喃骨架的亚胺胍衍生物及其制备和应用 - Google Patents

一种含有呋喃骨架的亚胺胍衍生物及其制备和应用 Download PDF

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WO2019101160A1
WO2019101160A1 PCT/CN2018/117144 CN2018117144W WO2019101160A1 WO 2019101160 A1 WO2019101160 A1 WO 2019101160A1 CN 2018117144 W CN2018117144 W CN 2018117144W WO 2019101160 A1 WO2019101160 A1 WO 2019101160A1
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furan
bisimine
oxime
tetrahydrate
solvates
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French (fr)
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邹永
刘洁
罗翔
盛剑飞
宋现恒
位文涛
李建恒
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中山大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2053—Other nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to the fields of chemical industry and environmental protection, in particular to an imine oxime derivative containing a furan skeleton, and preparation and application thereof.
  • CO 2 capture, utilization and storage (CCUS) technology is a direct emission reduction technology that is extremely important for stabilizing the concentration of carbon dioxide in the atmosphere.
  • the most critical and primary step is the CO 2 capture technology (Chem.Rev). .2016, 116, 11840-11876; Energy Technology Economics, 2010, 22(4), 21-26; Low Carbon World, 2013, 3(1), 30-33).
  • the chemical absorption method of CO 2 is an important and effective CO 2 capture method.
  • Typical chemical absorbents are alkyl alcohol amines and hot potash solutions, etc., which utilizes CO 2 as an acid.
  • the nature of the gas is absorbed by an alkaline substance and then desorbed by heating to achieve the purpose of concentrated enrichment of CO 2 ; however, the disadvantage of this method is that the absorbent is energy-regenerating, easily degradable, volatile, and Corrosive and so on.
  • CO 2 capture technology is related to other acid gas (such as SO 2 , SO 3 , NO 2 , H 2 S, etc.) and anion capture technology (Angew.Chem.Int.Ed.2015,54,10525 -10529), is expected to produce application value in multiple fields.
  • the object of the present invention is to overcome the shortcomings in the prior art, and to provide an environment friendly, low cost, simple process, 2,5-furan bisimine oxime containing a furan structural unit (FuBIG, structural formula 1) and Accepted salts and solvates thereof, wherein the furan structural unit is derived from a renewable resource.
  • FuBIG furan structural unit
  • Another object of the present invention is to provide a process for the preparation of the above 2,5-furandiimimine.
  • a further object of the present invention is to provide a use of the above 2,5-furodiimine oxime as an anionic precipitant.
  • the above-mentioned 2,5-furobisimidoguanidine acceptable salts and solvates thereof include, but are not limited to, carbonates and solvates thereof, sulfites and solvates thereof, hydrochlorides and solvates thereof , sulfides and solvates thereof, sulfates and solvates thereof, nitrates and solvates thereof, phosphates and solvates thereof, hypochlorites and solvates thereof, perchlorates and their Solvates, dichromates and solvates thereof, permanganates and solvates thereof.
  • the solvates include, but are not limited to, hydrates, methanolates, and ethanolates.
  • the preparation method of the above 2,5-furanimine oxime comprises the steps of: reacting 2,5-furandialdehyde as a raw material with aminoguanidine hydrochloride in solvent A; after completion of the reaction, the reaction solution is at a certain temperature The mixture was allowed to stand and filtered to obtain 2,5-furanimine hydrochloride. After alkalization, it was allowed to stand twice to obtain 2,5-furanimide.
  • the 2,5-furandicarbaldehyde is prepared by using the renewable biomass resource 5-hydroxymethylfurfural as a raw material (see, in particular, Chem. Rev. 2013, 113, 1499-1597).
  • the molar ratio of the 2,5-furandicarbaldehyde to aminoguanidine hydrochloride is from 1:1 to 1:3, preferably in a molar ratio of 1:2.
  • the molar ratio of the 2,5-furan bis iminium hydrochloride to the base is from 1:2 to 1:4, preferably in a molar ratio of 1:2.
  • the solvent A may be, but not limited to, methanol, ethanol, 1,4-dioxane or tetrahydrofuran; preferably the solvent is methanol or ethanol.
  • the reaction temperature is 60 to 100 ° C, preferably the reaction temperature is 70 ° C; the reaction time is 6 to 24 hours, preferably the reaction time is 12 hours.
  • the temperature at which the reaction liquid is allowed to stand is 0 to 40 ° C, preferably 0 to 10 ° C, more preferably 4 ° C; and the standing time is 0.5 to 12 hours.
  • the alkalization, the base used may be, but not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or cesium carbonate.
  • the secondary standing temperature is 0 to 40 ° C, preferably 0 to 10 ° C, more preferably 4 ° C; and the standing time is 0.5 to 12 hours.
  • the use of the 2,5-furodiimine oxime as an acid gas absorbent is carried out in a solvent B by contact with an acid gas or a mixed gas containing an acid gas to form a precipitate, and is filtered to obtain a precipitate A.
  • Precipitate A is a salt containing 2,5-furan bisimine oxime and an acid gas-related anion which has a very low liquid phase solubility. Heating the precipitate A to a certain temperature releases an acid gas and regenerates the 2,5-furanimide. The released acid gas can be collected, and the regenerated 2,5-furanimide can be contacted again with an acid gas or a mixed gas containing an acid gas, thereby repeating the above process. By circulating in this way, the acid gas is continuously enriched.
  • the acid gas includes, but is not limited to, carbon dioxide, sulfur dioxide, sulfur trioxide, nitrogen dioxide, nitrogen monoxide, nitrous oxide or hydrogen sulfide; the acid gas-containing mixed gas includes, but is not limited to, between the above acid gases. Mix in any ratio and mix one or more acid gases with air, nitrogen, oxygen or inert gas in any ratio.
  • the 2,5-furodisylamine is used as a carbon dioxide absorber for carbon dioxide capture, utilization and storage.
  • the solvent B is one of water, methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, 1,4-dioxane, sulfolane, N-methylpyrrolidone, polyethylene glycol dimethyl ether or propylene carbonate or More than one mixture; preferably solvent B is one or more mixtures of water, methanol or ethanol; more preferably solvent B is water, methanol, ethanol, 5 to 95% (v/v) aqueous methanol or 5 to 95 % (V/V) aqueous ethanol solution.
  • the precipitation temperature of the precipitate A is 25 to 180 ° C, preferably 40 to 120 ° C, and more preferably 40 to 100 ° C.
  • the use of the 2,5-furodiimine oxime as an anionic precipitant is in the solvent B, which can form a strong bond with an anion and form a precipitate.
  • Anions capable of forming precipitates thereof include, but are not limited to, carbonate, bicarbonate, sulfite, bisulfite, sulfate, hydrogen sulfate, nitrate, hydrogen sulfide, phosphate, hydrogen phosphate, dihydrogen phosphate Root, perchlorate, hypochlorite, dichromate or permanganate.
  • the salt of 2,5-furodiimine in the aqueous phase with an acid gas can be used as an efficient, controllable, low-energy acid gas release agent.
  • the salt of 2,5-furanimine in the aqueous phase with carbon dioxide can be used as a highly efficient, controllable, low-energy carbon dioxide gas release agent.
  • a carrier including but not limited to activated carbon, chitosan, silica gel, macroporous adsorption.
  • Resin, diatomaceous earth, organic framework materials, alumina, cyclodextrin, molecular sieves, zeolites form a solid phase absorbent, which also has the effect and ability to absorb acid gases.
  • the 2,5-furandiimine oxime of the present invention is a novel type of organic compound containing a furan skeleton, and has remarkable acid gas absorption characteristics and anion separation characteristics, and can be used for carbon dioxide capture, utilization, and storage. Air purification, pollution prevention, environmental protection and other fields.
  • the 2,5-furan bisimine oxime of the present invention can be easily regenerated and recycled after absorbing acid gas, and the regeneration energy consumption is low, the cost is lowered, and the efficiency is improved.
  • the key raw material for preparing 2,5-furanimine in the present invention 2,5-furandicarbaldehyde is prepared from a renewable biomass resource 5-hydroxymethylfurfural as a raw material, and therefore, the preparation method of the present invention Reduce the consumption of fossil resources, reduce carbon emissions, and facilitate sustainable development and application.
  • the preparation method of the 2,5-furan bisimine oxime of the invention is simple, the conditions are mild, the reaction time is short, the yield is high, the cost is low, and the scale preparation is easy to be realized.
  • Figure 1 shows the nuclear magnetic resonance spectrum (400 MHz, DMSO-d 6 ) of 2,5-furan bis-imine oxime (FuBIG).
  • Figure 2 is a nuclear magnetic resonance carbon spectrum (100 MHz, DMSO-d 6 ) of 2,5-furodiimine oxime (FuBIG).
  • Figure 3 is an infrared spectrum of each substance collected by React IR in Example 32.
  • Figure 4 is a graph showing the relative change trend of the interconversion of 2,5-furodiimine oxime with 2,5-furan bisimine ruthenium tetrahydrate in Example 32.
  • Figure 5 is a graph showing the interconversion of 2,5-furodiimine oxime with 2,5-furan bisimine ruthenium tetrahydrate in Example 32.
  • Figure 6 is a graph showing the results of X-ray single crystal measurement of 2,5-furan bisimine hydrazine tetrahydrate of Example 33.
  • Figure 7 is an X-ray powder diffraction pattern of 2,5-furan bisimine ruthenium tetrahydrate of Example 34.
  • Figure 8 is a thermogravimetric infrared test chart of 2,5-furan bisimine hydrazine tetrahydrate of Example 35, wherein: Figure A is a thermogravimetric test chart; and Figure B is an infrared test chart.
  • Figure 9 is a graph showing the weight versus time of 50, 70, 80, 100, 120, 140, 160 ° C of 2,5-furan bisimine hydrazine tetrahydrate in Example 35, respectively.
  • Figure 10 is a test for solubility
  • A is an ultraviolet absorption spectrum of an aqueous solution of 5 ⁇ 10 -5 M 2,5-furan bisimine hydrazine hydrochloride in Example 37
  • B is 2,5-furan bisimine hydrazine hydrochloride. Standard curve for UV absorption of aqueous solutions.
  • 2,5-furandicarbaldehyde (12.4 g, 0.1 mol), aminoguanidine hydrochloride (22 g, 0.2 mol), and ethanol (100 ml) were placed in a reaction flask, stirred, and heated to 70 ° C for 12 hours. After completion of the reaction, the reaction solution was allowed to stand at 4 ° C for 12 hours, suction filtered, and the filter cake was washed three times with ethanol, and the filter cake was collected, and dried to give 34.7 g of pale yellow solid as 2,5-furan diimine hydrochloride.
  • Salt hydrate chemical formula: FuBIG ⁇ 2HCl ⁇ 2.5H 2 O, yield 98.0%; mp.184-190°C; elemental analysis, theoretical value: C: 27.13%; H: 5.41%; N: 31.64%; : C: 26.62%; H: 5.08%; N: 31.74%.
  • the mixture was poured into a reaction flask, and 100 ml of a 2 M aqueous sodium hydroxide solution was added thereto, and the mixture was stirred at room temperature for 0.5 hour, and allowed to stand at 4 ° C for 12 hours, suction-filtered, and dried to obtain 22.66 g of 2,5-furanimine. : 96%, melting point: 244-246 ° C.
  • the mixture was placed in a reaction flask, and 100 ml of a 2 M aqueous sodium hydroxide solution was added thereto, and the mixture was stirred at room temperature for 0.5 hour, and allowed to stand at 0 ° C for 10 hours, suction-filtered, and dried to obtain 21.24 g of 2,5-furanimine. 90%, melting point: 244-246 °C.
  • the mixture was placed in a reaction flask, and 100 ml of a 2 M sodium carbonate aqueous solution was added thereto, and the mixture was stirred at room temperature for 0.5 hour, and allowed to stand at 30 ° C for 3 hours, suction-filtered, and dried to obtain 21.24 g of 2,5-furanimine, yield 90. %, melting point: 244-246 ° C.
  • the mixture was placed in a reaction flask, and 100 ml of a 2 M potassium carbonate aqueous solution was added thereto, and the mixture was stirred at room temperature for 0.5 hour, and allowed to stand at 0 ° C for 12 hours, suction-filtered, and dried to obtain 21.95 g of 2,5-furanimine, yield 93. %, melting point: 244-246 ° C.
  • the mixture was poured into a reaction flask, and 100 ml of a 2 M aqueous sodium hydroxide solution was added thereto, and the mixture was stirred at room temperature for 0.5 hour, and then allowed to stand at 25 ° C for 1 hour, suction-filtered, and dried to obtain 19.59 g of 2,5-furanimine. The rate was 83%, and the melting point was 244-246 °C.
  • Example 13 Absorption of carbon dioxide in air by aqueous solution of 2,5-furan bisimine
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 200 ml of water, and the mixture was stirred under air for 3 hours at room temperature to precipitate a yellow solid, which was filtered with suction and dried to give 3.
  • 5-furan bis imine hydrazine tetrahydrate (FuBIGH 2 (CO 3 ) (H 2 O) 4 ), yield: 91%.
  • Example 14 Absorption of carbon dioxide in air by aqueous solution of 2,5-furan bisimine
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 100 ml of water, and the mixture was stirred for 12 hours at room temperature under full contact with air to precipitate a yellow solid, which was filtered with suction and dried to give a white powder.
  • - furan diimine hydrazine tetrahydrate (FuBIGH 2 (CO 3 ) (H 2 O) 4 ), weight 3.52 g, yield: 95%.
  • Example 15 Absorption of carbon dioxide in air by 2,5-furan bisimine hydrazine 50% aqueous ethanol solution
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 100 ml of 50% ethanol water, and the mixture was stirred under air for 12 hours at room temperature to precipitate a yellow solid, which was filtered and dried to give a yellow powder.
  • 2,5-furobisimine quinone tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ), weight 3.15 g, yield 85%.
  • Example 16 Absorption of carbon dioxide by 2,5-furan bisenimine 5% NaOH aqueous solution
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 100 ml of 5% methanol water, and the mixture was stirred for 1 hour at room temperature under a sufficient contact with carbon dioxide to precipitate a yellow solid, which was filtered and dried to give a yellow powder.
  • 2,5-furobisimine quinone tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ), weight 3.44 g, yield 93%.
  • Example 17 Absorption of carbon dioxide by 2,5-furan bisimine ⁇ 25% aqueous methanol solution
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 100 ml of 25% methanol water, and the mixture was stirred under air for 12 hours at room temperature to precipitate a yellow solid, which was filtered and dried to give a yellow powder.
  • 2,5-furobisimine hydrazine tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ), weight 3.16 g, yield 85%.
  • Example 18 Absorption of carbon dioxide by 2,5-furan bisimine hydrazine 50% aqueous methanol solution
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 100 ml of 50% methanol water, and the mixture was stirred under nitrogen for 1 hour at room temperature to precipitate a yellow solid.
  • - furan diimine hydrazine tetrahydrate (FuBIGH 2 (CO 3 ) (H 2 O) 4 ) powder weight 3.10 g, yield 84%.
  • Example 19 Absorption of carbon dioxide in air by 2,5-furan bisimine ⁇ 75% aqueous methanol solution
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 200 ml of a 75% aqueous methanol solution, and the mixture was stirred under air for 12 hours at room temperature to precipitate a yellow solid.
  • Example 20 Absorption of carbon dioxide by 2,5-furan bisimine hydrazine 95% aqueous methanol solution
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 250 ml of a 95% aqueous methanol solution, and the mixture was stirred under a full atmosphere of carbon dioxide for 1 hour at room temperature to precipitate a yellow solid.
  • Example 21 Absorption of sulfur dioxide by an aqueous solution of 2,5-furan bisimine
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 100 ml of water, sulfur dioxide gas was added thereto, and the mixture was stirred for 1 hour to precipitate a yellow solid, which was filtered with suction and dried to give yellow 2,5-furanimine oxime.
  • the sulfite powder has a chemical formula of FuBIGH 2 (SO 3 )(H 2 O) 4 and has a weight of 3.55 g and a yield of 91%.
  • Example 22 Absorption of hydrogen sulfide gas by an aqueous solution of 2,5-furan bisimine
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 100 ml of water, hydrogen sulfide gas was added thereto, and the mixture was stirred for 1 hour to precipitate a yellow solid, which was filtered with suction and dried to give yellow 2,5-furan diimine.
  • ⁇ sulfide powder which is FuBIG(H 2 S) 2 (H 2 O) 3.5 , weight 3.08 g, yield 84%; mp. 217-222 ° C; elemental analysis, theoretical value: C, 26.01; H, 6.82; N, 30.33; S, 17.36; Found: C: 26.32%; H: 5.16%; N: 30.11%; S: 18.90%.
  • Example 23 Absorption of nitrogen dioxide by an aqueous solution of 2,5-furan bisimine
  • 2,5-furobisimine oxime (2.36 g, 10 mmol) was dissolved in 100 water, and nitrogen dioxide gas was introduced thereto, and the mixture was stirred for 1 hour to precipitate a yellow solid, which was filtered with suction and dried to give yellow 2,5-furan.
  • Amine cerium nitrate powder having a chemical formula of FuBIGH 2 (NO 3 ) 2 (H 2 O) 2 and having a weight of 3.74 g and a yield of 94%.
  • Example 24 Absorption of sulfite ions by aqueous solution of 2,5-furan bisimine
  • Example 25 Absorption of sulfite ions by an aqueous solution of 2,5-furan bisimine
  • Example 26 Absorption of nitrate ions by aqueous solution of 2,5-furan bisimine
  • Example 27 Absorption of hydrogen phosphate ions by an aqueous solution of 2,5-furan bisimine
  • Example 28 Release of carbon dioxide by carbon dioxide 2,5-furan bis imine hydrazine tetrahydrate - absorption cycle experiment
  • 2,5-furan bis imine hydrazine tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ), 3.7 g, 10 mmol) was placed in a watch glass, heated at 100 ° C for 5 hours at normal pressure, and weighed. It was 2.46g and the weight loss was 33.6%.
  • the 2,5-furan diimine ruthenium tetrahydrate loses H 2 O and CO 2 to regenerate 2,5-furan bisimine oxime, and the theoretical weight loss is 36.22%.
  • the weight-retained solid was dissolved in water, and carbon dioxide gas was introduced thereto, and the mixture was stirred for 1 hour to precipitate a yellow solid, which was filtered with suction and dried to give 3.52 g of a powdery product of 2,5-furanimine yttrium tetrahydrate.
  • Example 29 Release-absorption cycle experiment of carbon dioxide by 2,5-furan bisimine hydrazine tetrahydrate
  • Example 30 Carbon dioxide release-absorption cycle experiment of 2,5-furan bisimine ruthenium tetrahydrate
  • Example 32 Kinetic experiment of carbon dioxide absorption by aqueous solution of 2,5-furan bis imine
  • a 100 ml two-necked flask was placed in an oil bath, magnetically stirred, and inserted into an in-line infrared Dicomp probe and fixed with a Teflon adapter.
  • 40 ml of a 42 mM aqueous solution of 2,5-furan bisimidoquinone was added to the flask, stirring was started and data collection of React IR was started (one data was collected every 0.5 min).
  • a carbon dioxide balloon was inserted into the other end of the flask and stirring was continued until the 2,5-furanimine oxime was completely converted to 2,5-furan bisimine ruthenium tetrahydrate.
  • the heating was started, and the temperature was gradually raised to 40, 50, 60, and 70 ° C, and the change of the substance in the reaction flask was observed.
  • Example 33 Preparation and X-ray diffraction analysis of 2,5-furan bisimine ruthenium tetrahydrate carbonate single crystal
  • Single crystal preparation 10 ml of an aqueous solution containing 0.01 M of 2,5-furodiimide was placed in a round bottom flask, opened, and allowed to stand at room temperature for one week to precipitate crystals, which were filtered to obtain a yellow single crystal.
  • Single crystal X-ray diffraction analysis Select a crystal with a suitable crystal size to adhere to a glass filament, and measure the single crystal structure using an X-ray single crystal diffractometer (Xcalibur Nova) with Cu-K ⁇ ray.
  • Xcalibur Nova X-ray single crystal diffractometer
  • the crystal test parameters are shown in Table 1.
  • A represents the molecular structure and chemical composition of 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) crystal, which is composed of a 2,5-furan double carbonate
  • the iminium (FuBIGH 2 CO 3 ) and four water molecules are formed by hydrogen bonding;
  • (2) B represents the first hydrogen bonding mode of CO 3 2- in the crystal molecule of 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ): CO 3 2- accepting 9 hydrogen bonds as a hydrogen bond acceptor, 5 of which are from water molecules and 4 are from sulfhydryl groups;
  • C represents 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) crystal molecule CO 3 2- second hydrogen bonding mode: CO 3 2 - accepting 9 hydrogen bonds for hydrogen bond acceptors, 3 of which are from water molecules and 6 from sulfhydryl groups;
  • D represents a hydrogen bond between CO 3 2- and water molecules in a crystal of 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) Minimum complete unit;
  • E represents a supramolecular molecule formed by hydrogen bonding of CO 3 2- and sulfhydryl groups in a crystal of 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) Plane structure
  • F represents a supramolecular structure formed by hydrogen bonding of a sulfhydryl group and a water molecule in a crystal of 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ).
  • Example 34 Powder diffraction experiment of 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 )
  • Figure 7 is an X-ray powder diffraction pattern of FuBIGH 2 (CO 3 )(H 2 O) 4 with X-ray powder diffraction at 2 ⁇ angle and interplanar spacing (d value) at about 6.85 (12.9), 7.87 ( 11.2), 8.67 (10.2), 13.48 (6.6), 15.27 (5.8), 15.87 (5.6), 19.05 (4.7), 19.77 (4.5), 21.06 (4.2), 24.45 (3.6), 25.75 (3.5), 27.75 ( 3.5), 27.98 (3.2) have characteristic peaks, and the 2 ⁇ angle allows an error of ⁇ 0.2°.
  • Table 2 The specific data is shown in Table 2:
  • Example 35 Thermogravimetric infrared experiment of 2,5-furan bis imine hydrazine tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 )
  • thermogravimetric infrared analysis experiment was carried out on 2,5-furan diimine ruthenium tetrahydrate, the temperature range was 25-800 ° C, and the heating rate was 10 K/min.
  • the green line of Fig. A is the thermogravimetric curve of 2,5-furan bisimine quinone tetrahydrate.
  • the theoretical weight loss of 2,5-furan diimine hydrazine tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) lost H 2 O and CO 2 regeneration 2,5-furan bis imin oxime was 36.22%.
  • the carbon dioxide 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) has the highest weight loss rate at 100 ° C, and water molecules and carbon dioxide molecules at 165 ° C. Total weight loss, reaching 36.31%.
  • Figure B is an infrared spectrum of a 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) eutectic compound as a function of time and temperature in a nitrogen atmosphere, as seen from Figure 8B.
  • the molecule releases water molecules and carbon dioxide molecules under heating conditions, and the water molecules and carbon dioxide molecules are released simultaneously.
  • Example 36 Thermochemical thermogravimetric experiment of 2,5-furan bis imine hydrazine tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 )
  • Constant temperature thermogravimetric analysis of 2,5-furan bis-imine ruthenium tetrahydrate was carried out, and the weights were respectively tested at 50 ° C, 70 ° C, 80 ° C, 100 ° C, 120 ° C, 140 ° C, 160 ° C.
  • the 2,5-furan bisimine ruthenium tetrahydrate lost H 2 O and CO 2 regenerated 2,5-furan bis imine oxime theoretical weight loss 36.22%, as shown by the black line in the figure.
  • the rate of loss of H 2 O and CO 2 is different at different temperatures, and the higher the temperature, the faster the rate of weight loss. The shorter the time to reach equilibrium. When the temperature is greater than 100 ° C, the weight loss is close to the theoretical value.
  • Example 37 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) solubility product and 2,5-furan bis imine hydrazine hydrochloride, nitrate Determination of solubility of sulfites and sulfates
  • the pH of the aqueous solution of saturated carbonic acid 2,5-furan bisimine ruthenium tetrahydrate (FuBIGH 2 (CO 3 )(H 2 O) 4 ) was determined by a pH meter to be 8.01 (2), and the pKa of HCO 3 - was known to be 10.32.

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Abstract

本发明公开了一种含有呋喃骨架的亚胺胍衍生物，包括2,5-呋喃双亚胺胍和2,5-呋喃双亚胺胍可接受的盐及其溶剂合物；还公开了2,5-呋喃双亚胺胍的制备方法，及其作为酸性气体吸收剂、阴离子沉淀剂的用途。本发明的2,5-呋喃双亚胺胍在吸收酸性气体后能方便地再生并循环使用，其再生能耗低，降低了成本、提高了效率，其制备方法简单、条件温和、反应时间短、收率高、成本低，易于实现规模化制备。

Description

一种含有呋喃骨架的亚胺胍衍生物及其制备和应用 技术领域
本发明涉及化工和环保领域，特别涉及一种含有呋喃骨架的亚胺胍衍生物及其制备和应用。
背景技术
随着经济社会的发展，化石原料使用所导致的温室效应及空气污染已严重地威胁着人类赖以生存的环境，全球气候变暖、温室效应和环境污染是各国可持续发展面临的共同挑战。研究表明，大气中的二氧化碳含量因人类活动而不断增加，二氧化碳浓度已经从工业革命前的280ppm上升到目前超过400ppm，由此造成大气温室效应加剧，平均地表气温升高，全球气候变暖，相关自然灾害发生频率和强度增加。这种全球性气候变化已经严重威胁到人类社会的生存及发展，以CO 2为代表的温室气体减排问题刻不容缓。
CO 2的捕集、利用与封存(CCUS)技术是一种直接减排技术，对稳定大气中二氧化碳的浓度极为重要，其中非常关键的、首要的步骤是CO 2的捕集技术(Chem.Rev.2016,116,11840-11876；能源技术经济,2010,22(4),21-26；低碳世界,2013,3(1),30-33)。在此类技术中，CO 2的化学吸收法是一类重要且行之有效的CO 2捕集方法，典型的化学吸收剂为烷基醇胺和热钾碱溶液等，它是利用CO 2为酸性气体的性质，采用碱性物质进行吸收，然后加热使其解吸，从而达到集中富集CO 2的目的；但该方法的缺点是吸收剂再生能耗大、易降解、易挥发，而且对设备的腐蚀性强等。
利用可再生资源代替化石资源制备各类化学品(包括燃料、基本化工原料、精细化学品及药品等)是一种重要的、具有代表性的低碳减排技术，已在生物质能源等领域形成大规模应用，产生了良好的社会和经济效益(Environ.Sci.Technol.,2017,51,3575-3583；Angew.Chem.Int.Ed.,2007,46,5056-5058；中外能源,2014,19,21-26)。如果在碳捕集技术中基于可再生资源进行CO 2化学吸收剂的设计合成及开发应用，则该吸收剂本身的制备和应用不产生或较少产生化石资源的消耗和碳排放，这对高效地实现CO 2的捕集、利用与封存十分有利。同时，CO 2捕集技术与其它酸性气体(如SO 2、SO 3、NO 2、H 2S等)及阴离子的捕集技术具有相关性(Angew.Chem.Int.Ed.2015,54,10525-10529)，有望在多个领域产生应用价值。
发明内容
本发明的目的在于克服现有技术中存在的缺点，提供一种环境友好、成本低、工艺简单的含有呋喃结构单元的2,5-呋喃双亚胺胍(简称FuBIG，结构式1)及其可接受的盐及其溶剂合物，其中的呋喃结构单元来自于可再生资源。
本发明的另一目的在于提供一种上述2,5-呋喃双亚胺胍的制备方法。
本发明的又一目的在于提供一种上述2,5-呋喃双亚胺胍作为酸性气体吸收剂的用途。
本发明的再一目的在于提供一种上述2,5-呋喃双亚胺胍作为阴离子沉淀剂的用途。
本发明的目的通过下述技术方案实现：
一种2,5-呋喃双亚胺胍化合物，具有以下结构式：
Figure PCTCN2018117144-appb-000001
上述2,5-呋喃双亚胺胍可接受的盐及其溶剂合物，包括但不限于：碳酸盐及其溶剂合物、亚硫酸盐及其溶剂合物、盐酸盐及其溶剂合物、硫化物及其溶剂合物、硫酸盐及其溶剂合物、硝酸盐及其溶剂合物、磷酸盐及其溶剂合物、次氯酸盐及其溶剂合物、高氯酸盐及其溶剂合物、重铬酸盐及其溶剂合物、高锰酸盐及其溶剂合物。所述溶剂合物包括但不限于水合物、甲醇合物、乙醇合物。
上述2,5-呋喃双亚胺胍的制备方法，包括下述步骤：以2,5-呋喃二甲醛为原料，与盐酸氨基胍在溶剂A中反应；反应完成后，将反应液在一定温度下静置，过滤，得到2,5-呋喃双亚胺胍盐酸盐；再经碱化，二次静置，得到2,5-呋喃双亚胺胍。
所述2,5-呋喃二甲醛是以可再生生物质资源5-羟甲基糠醛为原料制备得到(具体参见：Chem.Rev.2013,113,1499-1597)。
所述2,5-呋喃二甲醛与盐酸氨基胍的摩尔比为1:1～1:3，优选摩尔比为1:2。
所述2,5-呋喃双亚胺胍盐酸盐与碱的摩尔比为1:2～1:4，优选摩尔比为1:2。
所述溶剂A可以但不限于是甲醇、乙醇、1,4-二氧六环或四氢呋喃；优选溶剂为甲醇或乙醇。
所述的反应温度为60～100℃，优选反应温度为70℃；反应时间为6～24小时，优选反应时间为12小时。
所述反应液静置的温度为0～40℃，优选温度为0～10℃，更优选温度为4℃；静置的时间为0.5～12小时。
所述碱化，采用的碱可以但不限于是氢氧化钠、氢氧化钾、碳酸钠、碳酸钾或碳酸铯。
所述的二次静置的温度为0～40℃，优选温度为0～10℃，更优选温度为4℃；静置的时 间为0.5～12小时。
所述2,5-呋喃双亚胺胍作为酸性气体吸收剂的用途，是在溶剂B中，经与酸性气体或含酸性气体的混合气体接触，形成沉淀析出，过滤，得到沉淀A。沉淀A是含有2,5-呋喃双亚胺胍及酸性气体相关阴离子的盐，此盐具有很低的液相溶解性。将沉淀A加热至一定温度，可释放出酸性气体，并使2,5-呋喃双亚胺胍再生。所释放的酸性气体可进行收集，再生得到的2,5-呋喃双亚胺胍可再次与酸性气体或含酸性气体的混合气体接触，从而重复上述过程。这样循环往复，可使酸性气体不断得到富集。
所述酸性气体包括但不限于二氧化碳、二氧化硫、三氧化硫、二氧化氮、一氧化氮、一氧化二氮或硫化氢；所述含酸性气体的混合气体包括但不限于上述酸性气体之间以任意比例混合，以及一种或多种酸性气体与空气、氮气、氧气或惰性气体以任意比例混合。
所述2,5-呋喃双亚胺胍作为二氧化碳吸收剂，用于二氧化碳捕获、利用及封存。
所述溶剂B是水、甲醇、乙醇、丙酮、四氢呋喃、乙腈、1,4-二氧六环、环丁砜、N-甲基吡咯烷酮、聚乙二醇二甲醚或碳酸丙烯酯中的一种或一种以上混合物；优选溶剂B为水、甲醇或乙醇中的一种或一种以上混合物；更优选溶剂B为水、甲醇、乙醇、5～95％(V/V)甲醇水溶液或5～95％(V/V)乙醇水溶液。
所述沉淀A的加热温度为25～180℃，优选温度为40～120℃，更优选为40～100℃。
所述2,5-呋喃双亚胺胍作为阴离子沉淀剂的用途，是在溶剂B中，可与阴离子产生强的结合作用并形成沉淀析出。能与其形成沉淀的阴离子包括但不限于碳酸根、碳酸氢根、亚硫酸根、亚硫酸氢根、硫酸根、硫酸氢根、硝酸根、硫化氢根、磷酸根、磷酸氢根、磷酸二氢根、高氯酸根、次氯酸根、重铬酸根或高锰酸根。
此外，2,5-呋喃双亚胺胍在水相中与酸性气体形成的盐，可以作为高效、可控、低能耗的酸性气体释放剂的用途。特别的，2,5-呋喃双亚胺胍在水相中与二氧化碳形成的盐，可以作为高效、可控、低能耗的二氧化碳气体释放剂的用途。
需提及的是，鉴于2,5-呋喃双亚胺胍对酸性气体有良好吸收效果和结合能力，将其负载或分散于载体(包括但不限于活性炭、壳聚糖、硅胶、大孔吸附树脂、硅藻土、有机骨架材料、氧化铝、环糊精、分子筛、沸石)上，形成固相吸收剂，也同样具有吸收酸性气体的效果和能力。
本发明涉及的过程如下：
Figure PCTCN2018117144-appb-000002
本发明与现有技术相比具有如下优点和效果：
(1)本发明的2,5-呋喃双亚胺胍是一类新型的、含有呋喃骨架的有机化合物，具有显著的酸性气体吸收特性及阴离子分离特性，可用于二氧化碳捕集、利用与封存，空气净化、污染防治、环境保护等领域。
(2)本发明的2,5-呋喃双亚胺胍在吸收酸性气体后能方便地再生并循环使用，其再生能耗低，降低了成本、提高了效率。
(3)本发明制备2,5-呋喃双亚胺胍的关键原料2,5-呋喃二甲醛系由可再生生物质资源5-羟甲基糠醛为原料制备得到，因此，本发明的制备方法减少了化石资源的消耗，减少了碳排放，且利于实现可持续的开发和应用。
(4)本发明2,5-呋喃双亚胺胍的制备方法简单、条件温和、反应时间短、收率高、成本低，易于实现规模化制备。
附图说明
图1为2,5-呋喃双亚胺胍(FuBIG)的核磁共振氢谱(400MHz,DMSO-d 6)。
图2为2,5-呋喃双亚胺胍(FuBIG)的核磁共振碳谱(100MHz,DMSO-d 6)。
图3为实施例32中通过React IR收集各物质的红外光谱。
图4为实施例32中2,5-呋喃双亚胺胍与碳酸2,5-呋喃双亚胺胍四水合物相互转化的相对变化趋势图。
图5为实施例32中2,5-呋喃双亚胺胍与碳酸2,5-呋喃双亚胺胍四水合物的相互转化图。
图6为实施例33中碳酸2,5-呋喃双亚胺胍四水合物的X-射线单晶测试结果。
图7为实施例34中碳酸2,5-呋喃双亚胺胍四水合物的X-射线粉末衍射图。
图8为实施例35中碳酸2,5-呋喃双亚胺胍四水合物的热重红外测试图，其中：图A为热重测试图；图B为红外测试图。
图9为实施例35中碳酸2,5-呋喃双亚胺胍四水合物分别在50，70，80，100，120，140，160℃下重量随时间的变化曲线。
图10为溶解度的测试，A为实施例37中5×10 -5M 2,5-呋喃双亚胺胍盐酸盐水溶液紫外吸收图谱，B为2,5-呋喃双亚胺胍盐酸盐水溶液紫外吸收的标准曲线。
具体实施方式
下面结合实施例对本发明做进一步详细的描述，但本发明的实施方式不限于此。
实施例1：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至70℃，反应12小时。反应完毕后，将反应液在4℃下静置12小时，抽滤，用乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体34.7g，为2,5-呋喃双亚胺胍盐酸盐水合物，化学式为FuBIG·2HCl·2.5H 2O，收率98.0％；mp.184-190℃；元素分析，理论值：C:27.13％；H:5.41％；N:31.64％；实测值：C:26.62％；H:5.08％；N:31.74％。将其投入反应瓶中，加入2M氢氧化钠水溶液100ml，室温下搅拌0.5小时，在4℃下静置12小时，抽滤，干燥，得2,5-呋喃双亚胺胍22.66g，收率：96％，熔点：244-246℃。 1H NMR(400MHz,DMSO-d 6)δ7.83(s,1H),6.67(s,1H),5.84(s,2H),5.58(s,2H)(如图1所示)； 13C NMR(100MHz,DMSO-d 6)δ160.74,152.31,133.76,111.38(如图2所示)。
实施例2：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，四氢呋喃(100ml)加入反应瓶中，搅拌，加热至66℃，反应12小时。反应完毕后，将反应液在4℃下静置12小时，抽滤，用四氢呋喃洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M氢氧化钠水溶液100ml，室温下搅拌0.5小时，在4℃下静置12小时，抽滤，干燥，得2,5-呋喃双亚胺胍21.72g，收率92％，熔点：244-246℃。
实施例3：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，甲醇(100ml)加入反应瓶中，搅拌，加热至65℃，反应12小时，反应完毕后，将反应液在4℃下静置6小时，抽滤，用甲醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M氢氧化钠水溶液100ml，室温下搅拌0.5小时，在0℃下静置10小时，抽滤，干燥，得到2,5-呋喃双亚胺胍21.24g，收率90％，熔点：244-246℃。
实施例4：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至60℃，反应10小时，反应完毕后，将反应液在4℃下静置6小时，抽滤，用乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M氢氧化钾水溶液100ml，室温下搅拌0.5小时，在10℃下静置6小时，抽滤，干燥，得到2,5-呋喃双亚胺胍21.0g，收率89％，熔点：244-246℃。
实施例5：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，1,4-二氧六环(100ml)加入反应瓶中，搅拌，加热至80℃，反应12小时，反应完毕后，将反应液在4℃下静置12小时，抽滤，用1,4-二氧六环洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M碳酸钠水溶液100ml，室温下搅拌0.5小时，在30℃下静置3小时，抽滤，干燥，得到2,5-呋喃双亚胺胍21.24g，收率90％，熔点：244-246℃。
实施例6：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至70℃，反应6小时，反应完毕后，将反应液在4℃下静置12小时，抽滤，用乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M碳酸钾水溶液100ml，室温下搅拌0.5小时，在0℃下静置12小时，抽滤，干燥，得到2,5-呋喃双亚胺胍21.95g，收率93％，熔点：244-246℃。
实施例7：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至70℃,反应18小时，反应完毕后，将反应液在4℃下静置6小时，抽滤，用乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M氢氧化钠水溶液100ml，室温下搅拌0.5小时，再在25℃下静置1小时，抽滤，干燥，得到2,5-呋喃双亚胺胍19.59g，收率83％，熔点：244-246℃。
实施例8：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至70℃，反应12小时，反应完毕后，将反应液在室温下静置12小时，抽滤，用乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺 胍盐酸盐。将其投入反应瓶中，加入2M氢氧化钠水溶液100ml，室温下搅拌0.5小时，在4℃下静置12小时抽滤，干燥，得到2,5-呋喃双亚胺胍20.53g，收率87％，熔点：244-246℃。
实施例9：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至70℃，反应12小时，反应完毕后，将反应液在4℃下静置6小时，抽滤，用乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M氢氧化钠水溶液100ml，室温下搅拌0.5小时，在4℃下静置12小时抽滤，干燥，得到2,5-呋喃双亚胺胍20.06g，收率85％，熔点：244-246℃。
实施例10：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至70℃，反应12小时，反应完毕后，将反应液在4℃下静置12小时，抽滤，用乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M氢氧化钾水溶液100ml，室温下搅拌0.5小时，在4℃下静置12小时抽滤，干燥，得到2,5-呋喃双亚胺胍20.48g，收率91％，熔点：244-246℃。
实施例11：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至70℃，反应12小时，反应完毕后，将反应液在4℃下静置12小时，抽滤，用乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M碳酸钠水溶液100ml，室温下搅拌0.5小时，在40℃下静置12小时，抽滤，干燥，得到2,5-呋喃双亚胺胍14.89g，收率63％，熔点：244-246℃。
实施例12：2,5-呋喃双亚胺胍的制备
将2,5-呋喃二甲醛(12.4g，0.1mol)，盐酸氨基胍(22g，0.2mol)，乙醇(100ml)加入反应瓶中，搅拌，加热至70℃，反应12小时，反应完毕后，将反应液在4℃下静置0.5小时，抽滤，乙醇洗涤滤饼三次，收集滤饼，干燥后得到淡黄色固体，为2,5-呋喃双亚胺胍盐酸盐。将其投入反应瓶中，加入2M碳酸钾水溶液，室温下搅拌0.5小时，在4℃下静置3小时，抽滤，干燥，得到2,5-呋喃双亚胺胍15.58g，收率66％，熔点：244-246℃。
实施例13：2,5-呋喃双亚胺胍水溶液对空气中二氧化碳的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于200ml水中，与空气充分接触下，室温搅拌3小时，析出黄色固体，抽滤，干燥，得到黄色粉末3.37g，为碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)，收率：91％。
实施例14：2,5-呋喃双亚胺胍水溶液对空气中二氧化碳的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于100ml水中，与空气充分接触下，室温搅拌12小时，析出黄色固体，抽滤，干燥，得到黄色粉末，为碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)，重量3.52g，收率：95％。
实施例15：2,5-呋喃双亚胺胍50％乙醇水溶液对空气中二氧化碳的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于100ml 50％乙醇水中，与空气充分接触下，室温搅拌12小时，析出黄色固体，抽滤，干燥，得到黄色粉末，为碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)，重量3.15g，收率85％。
实施例16：2,5-呋喃双亚胺胍5％甲醇水溶液对二氧化碳的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于100ml 5％甲醇水中，与二氧化碳充分接触下，室温搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色粉末，为碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)，重量3.44g，收率93％。
实施例17：2,5-呋喃双亚胺胍25％甲醇水溶液对二氧化碳的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于100ml 25％甲醇水中，与空气充分接触下，室温搅拌12小时，析出黄色固体，抽滤，干燥，得到黄色粉末，为碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)，重量3.16g，收率85％。
实施例18：2,5-呋喃双亚胺胍50％甲醇水溶液对二氧化碳的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于100ml 50％甲醇水中，与二氧化碳充分接触下，室温搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)粉末，重量3.10g，收率84％。
实施例19：2,5-呋喃双亚胺胍75％甲醇水溶液对空气中二氧化碳的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于200ml 75％甲醇水溶液中，与空气充分接触下，室温搅拌12小时，析出黄色固体，抽滤，干燥，得到黄色碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)粉末，重量3.12g，收率84％。
实施例20：2,5-呋喃双亚胺胍95％甲醇水溶液对二氧化碳的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于250ml 95％甲醇水溶液中，与二氧化碳充分接触下，室温搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)粉末，重量3.33g，收率90％。
实施例21：2,5-呋喃双亚胺胍水溶液对二氧化硫的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于100ml水中，通入二氧化硫气体，搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色2,5-呋喃双亚胺胍亚硫酸盐粉末，化学式为FuBIGH 2(SO 3)(H 2O) 4，重量3.55g，收率91％。
实施例22：2,5-呋喃双亚胺胍水溶液对硫化氢气体的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于100ml水中，通入硫化氢气体，搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色2,5-呋喃双亚胺胍硫化物粉末，为FuBIG(H 2S) 2(H 2O) 3.5，重量3.08g，收率84％；mp.217-222℃；元素分析，理论值：C,26.01；H,6.82；N,30.33；S,17.36；实测值：C:26.32％；H:5.16％；N:30.11％；S:18.90％。
实施例23：2,5-呋喃双亚胺胍水溶液对二氧化氮的吸收
将2,5-呋喃双亚胺胍(2.36g，10mmol)溶于100水中，通入二氧化氮气体，搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色2,5-呋喃双亚胺胍硝酸盐粉末，化学式为FuBIGH 2(NO 3) 2(H 2O) 2，重量3.74g，收率94％。
实施例24：2,5-呋喃双亚胺胍水溶液对亚硫酸根离子的吸收
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液50ml，0.05M无水亚硫酸钠的水溶液50ml，加入到反应瓶中，搅拌2小时，抽滤，干燥，得黄色粉末0.94g，为FuBIGH 2(SO 3)(H 2O) 4，收率96.0％；mp.254-261℃；元素分析，理论值：C:24.61％；H:5.64％；N:28.72％；S:8.21％；实测值：C:24.73％；H:5.18％；N:28.56％；S:8.20％。
实施例25：2,5-呋喃双亚胺胍水溶液对亚硫酸根离子的吸收
量取0.05M 2,5-呋喃双亚胺胍的水溶液50ml，0.05M无水亚硫酸钠的水溶液50ml，加入到反应瓶中，搅拌2小时，抽滤，干燥，得黄色粉末0.87g，为FuBIGH 2(SO 3)(H 2O) 4，收率94.0％。
实施例26：2,5-呋喃双亚胺胍水溶液对硝酸根离子的吸收
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液50ml，0.1M硝酸钠的水溶液50ml，加入到反应瓶中，搅拌2小时，抽滤，干燥，得白色粉末0.90g，为FuBIGH 2(NO 3) 2(H 2O) 2，收率90.6％；mp.195-204℃；元素分析，理论值：C:24.12％；H:4.56％；N:35.17％；实测值：C:24.23％；H:4.31％；N:34.74％。
实施例27：2,5-呋喃双亚胺胍水溶液对磷酸氢根离子的吸收
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液50ml，0.05M磷酸氢二钠的水溶液50ml，加入到反应瓶中，搅拌2小时，抽滤，干燥，得白色粉末0.99g，为FuBIGH 2(H 2PO 4) 2(H 2O)，收率88.0％；mp.188-197℃；元素分析:理论值C:27.84％；H:5.26％；N:32.46％。实测值C:26.22％；H:5.76％；N:33.11％。
实施例28：碳酸2,5-呋喃双亚胺胍四水合物对二氧化碳的释放-吸收循环实验
碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)，3.7g，10mmol)置于表面皿中，常压100℃下加热5小时，称重为2.46g，失重33.6％。碳酸2,5-呋喃双亚胺胍四水合物失去H 2O和CO 2再生2,5-呋喃双亚胺胍，理论失重36.22％。将失重后的固体溶于水中，通入二氧化碳气体，搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色碳酸2,5-呋喃双亚胺胍四水合物粉末3.52g。
本实验表明：碳酸2,5-呋喃双亚胺胍四水合物经加热可释放出CO 2和H 2O，并使2,5-呋喃双亚胺胍再生；再生后的2,5-呋喃双亚胺胍可继续吸收CO 2并形成碳酸2,5-呋喃双亚胺胍四水合物。
实施例29：碳酸2,5-呋喃双亚胺胍四水合物对二氧化碳的释放-吸收循环实验
碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4，3.7g，10mmol)置于表面皿中，常压70℃下加热12小时，称重为2.6g，失重29.7％。将失重后的固体溶于水中，通入二氧化碳气体，搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色碳酸2,5-呋喃双亚胺胍四水合物粉末3.56g。
实施例30：碳酸2,5-呋喃双亚胺胍四水合物对二氧化碳的释放-吸收循环实验
碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4，3.7g，10mmol)置于表面皿中，常压120℃下加热干燥12小时，称重为2.46g，失重33.7％。将失重后的固体溶于水中，通入二氧化碳气体，搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色碳酸2,5-呋喃双亚胺胍四水合物粉末3.54g。
实施例31：碳酸2,5-呋喃双亚胺胍四水合物对二氧化碳的释放-吸收循环实验
碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)，3.7g，10mmol)置于表面皿中，常压180℃下加热干燥12小时，称重为2.45g，失重33.7％。将失重后的固体溶于水中，通入二氧化碳气体，搅拌1小时，析出黄色固体，抽滤，干燥，得到黄色碳酸2,5-呋喃双亚胺胍四水合物粉末3.55g。
实施例32：2,5-呋喃双亚胺胍水溶液吸收二氧化碳的动力学实验
实验仪器：梅特勒-托利多在线红外分析仪(ReactIR 15)
操作步骤：
(1)通过在线红外分析仪收集各物质的红外光谱，如图3所示。由各物质图谱可以看出，2,5-呋喃双亚胺胍与其吸收二氧化碳后形成的碳酸2,5-呋喃双亚胺胍四水合物在1511-1655cm -1与1280-1400cm -1(即碳酸根吸收波段)处有最小重叠，因此选择1533cm -1来跟踪2,5-呋喃双亚胺胍的变化，选择1361cm -1来跟踪碳酸2,5-呋喃双亚胺胍四水合物的变化。
(2)以在线红外分析仪监测2,5-呋喃双亚胺胍与碳酸2,5-呋喃双亚胺胍四水合物的循环转化过程。
将100ml双口烧瓶置于油浴中，加入磁力搅拌，一口插入在线红外Dicomp探头并用聚四氟乙烯适配器固定。在收集完实验背景后向烧瓶中加入42mM的2,5-呋喃双亚胺胍水溶液40ml，启动搅拌并开始React IR的数据收集(每间隔0.5min采集一个数据)。待数据稳定后，在烧瓶的另一口插入二氧化碳气球，继续搅拌，直至2,5-呋喃双亚胺胍完全转化为碳酸2,5-呋喃双亚胺胍四水合物。启动加热，逐渐升温至40、50、60、70℃，观测反应瓶中物质的变化。
数据分析：如图4、图5所示，选择1365cm -1处对碳酸2,5-呋喃双亚胺胍四水合物变化进行跟踪，选择1533cm -1处对2,5-呋喃双亚胺胍变化进行跟踪。由1365cm -1和1533cm -1相对变化趋势图可知，当向烧瓶通入CO 2后，反应液中的CO 3 2-浓度以较快的速度上升，而2,5-呋喃双亚胺胍的浓度以相对应的速度下降。约1.5h后，2,5-呋喃双亚胺胍水溶液对CO 2的吸收达到饱和，并且大量固体(即碳酸2,5-呋喃双亚胺胍四水合物)从溶液中析出。当析出完全后，启动加热，随着温度的逐渐升高，碳酸2,5-呋喃双亚胺胍四水合物逐渐转化为2,5-呋喃双亚胺胍并释放出CO 2，并且随着温度的升高转化速率逐渐加快。由在线红外分析数据可知，加热条件下碳酸2,5-呋喃双亚胺胍四水合物能较快的转化为2,5-呋喃双亚胺胍；数据显示，55℃时，碳酸2,5-呋喃双亚胺胍四水合物转化为2,5-呋喃双亚胺胍的速率达最大值。
实施例33：碳酸2,5-呋喃双亚胺胍四水合物单晶制备及X-射线衍射分析
单晶制备：将含0.01M 2,5-呋喃双亚胺胍的水溶液10ml加入到圆底烧瓶中，敞口，室温静置一个星期，析出晶体，过滤，得黄色单晶。
单晶X-射线衍射分析：选取大小合适晶型较好的晶体粘于一根玻璃丝上，使用X射线单晶衍射仪(Xcalibur Nova)进行单晶结构测定，用Cu-Kα射线
Figure PCTCN2018117144-appb-000003
作为光源，在T＝100K下，在2θ max＝134°范围内收集12423个衍射点，5860个独立衍射点(R int＝0.0204，R sigma＝0.0213)，晶体结构采用XS(Sheldrick，2008)解析，ShelXL(Sheldrick，2015)进行精修。证实该单晶为碳酸2,5-呋喃双亚胺胍四水合物，其化学式为FuBIGH 2(CO 3)(H 2O) 4。晶体测试参数如表1所示。
表1碳酸2,5-呋喃双亚胺胍四水合物的晶体测试参数
Figure PCTCN2018117144-appb-000004
Figure PCTCN2018117144-appb-000005
如图6所示：
(1)A表示碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)晶体的分子结构及化学组成，是由一个碳酸2,5-呋喃双亚胺胍(FuBIGH 2CO 3)和四个水分子经氢键作用构建而成；
(2)B表示碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)晶体分子中CO 3 2-的第一种氢键作用模式：CO 3 2-作为氢键受体接受9个氢键，其中5个来自水分子，4个来自胍基；
(3)C表示碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)晶体分子中CO 3 2-第二种氢键作用模式：CO 3 2-为氢键受体接受9个氢键，其中3个来自水分子，6个来自胍基；
(4)D表示碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)晶体中CO 3 2-与水分子之间的氢键作用而形成的最小完整单元；
(5)E表示碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)晶体中CO 3 2-与胍基通过氢键作用而形成的超分子平面结构；
(6)F表示碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)晶体中胍基与水分子通过氢键作用而形成的超分子结构。
上述实验表明：2,5-呋喃双亚胺胍可与碳酸根及水分子形成复杂的氢键相互作用，2,5-呋喃双亚胺胍只作为氢键的供体，CO 3 2-只作为氢键的受体，每个CO 3 2-作为氢键受体接受9个氢键，存在两种接收氢键的模式(模式一：9个氢键中，其中5个供体来自水分子，4个供体来自胍基；模式二：9个氢键中，其中3个供体来自水分子，6个供体来自胍基)。水分子既作为氢键的供体也作为氢键的受体。呋喃环上的氧原子未接受氢键。
实施例34：碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)粉末衍射实验
实验仪器与条件：帕纳科锐影(Empyrean)X-射线衍射仪，使用Cu-Kα辐射，扫描范围：5°-80°，扫描速度：5°/min，步长：0.02°。将实施例33所得单晶样品碾磨成粉末进行实验。
图7为FuBIGH 2(CO 3)(H 2O) 4的X-射线粉末衍射图，以2θ角度和晶面间距(d值)表示的X-射线粉末衍射在约6.85(12.9)、7.87(11.2)、8.67(10.2)、13.48(6.6)、15.27(5.8)、15.87(5.6)、19.05(4.7)、19.77(4.5)、21.06(4.2)、24.45(3.6)、25.75(3.5)、 27.75(3.5)、27.98(3.2)有特征峰，2θ角度允许存在±0.2°的误差。具体数据如表2所示：
表2FuBIGH 2(CO 3)(H 2O) 4的X-射线粉末衍射数据
Figure PCTCN2018117144-appb-000006
实施例35：碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)热重红外实验
对碳酸2,5-呋喃双亚胺胍四水合物进行热重红外分析实验，温度范围：25-800℃，升温速率：10K/min。如图8所示，图A绿线为碳酸2,5-呋喃双亚胺胍四水合物的热重曲线。碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)失去H 2O和CO 2再生2,5-呋喃双亚胺胍的理论失重36.22％。从图8A可知，碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)在100℃时失重速率值最大，在165℃时水分子和二氧化碳分子完 全失重，达到36.31％。图B为碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)共晶化合物在氮气氛围随时间和温度变化的红外谱图，由图8B可知，此分子在加热条件下可释放出水分子和二氧化碳分子，水分子和二氧化碳分子接近同时释放。
以上实验表明，碳酸2,5-呋喃双亚胺胍四水合物极易释放出H 2O和CO 2，相对于碳酸钙需要900℃以上的高温焙烧才能释放出CO 2，本发明所述方法能大幅度降低释放CO 2的能耗。
实施例36：碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)恒温热重实验
对碳酸2,5-呋喃双亚胺胍四水合物进行恒温热重分析实验，分别测试其分别在50℃、70℃、80℃、100℃、120℃、140℃、160℃温度下重量随时间的变化关系。如图9所示，碳酸2,5-呋喃双亚胺胍四水合物失去H 2O和CO 2再生2,5-呋喃双亚胺胍理论失重36.22％，如图中黑色线条所示。在不同的温度下失去H 2O和CO 2速率不同，温度越高失重速率越快。达到平衡的时间越短。当温度大于100℃时失重接近理论值。
以上实验表明，碳酸2,5-呋喃双亚胺胍四水合物能在较短的时间内和较低的温度下释放出H 2O和CO 2。
实施例37：碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)溶度积和2,5-呋喃双亚胺胍盐酸盐、硝酸盐、亚硫酸盐、硫酸盐溶解度的测定
(1)2,5-呋喃双亚胺胍碳酸盐的制备
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液5ml，0.05M碳酸氢钠的水溶液5ml，加入到反应瓶中，搅拌2小时，抽滤，干燥得2,5-呋喃双亚胺胍碳酸盐，重60mg。
(2)2,5-呋喃双亚胺胍硫酸盐的制备
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液5ml，0.05M无水硫酸钠的水溶液5ml，加入到反应瓶中，搅拌2小时，抽滤，干燥得2,5-呋喃双亚胺胍硫酸盐，重30mg。
(3)2,5-呋喃双亚胺胍硝酸盐的制备
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液5ml，0.1M硝酸钠的水溶液5ml，加入到反应瓶中，搅拌2小时，抽滤，干燥得2,5-呋喃双亚胺胍硝酸盐，重68mg。
(4)2,5-呋喃双亚胺胍亚硫酸盐的制备
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液5ml，0.05M无水亚硫酸钠的水溶液5ml，加入到反应瓶中，搅拌2小时，抽滤，干燥得2,5-呋喃双亚胺胍亚硫酸盐，重59mg。
(5)2,5-呋喃双亚胺胍磷酸盐的制备
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液5ml，0.05M磷酸氢二钠的水溶液5ml，加入到反应瓶中，搅拌2小时，抽滤，干燥得2,5-呋喃双亚胺胍磷酸盐，重60mg。
(6)2,5-呋喃双亚胺胍硫化物的制备
量取0.05M 2,5-呋喃双亚胺胍盐酸盐的水溶液5ml，0.05M硫氢化钠的水溶液5ml，加入到反应瓶中，搅拌2小时，抽滤，干燥得2,5-呋喃双亚胺胍硫化物，重57mg。
(7)碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)溶度积和2,5-呋喃双亚胺胍盐酸盐、硝酸盐、亚硫酸盐、硫酸盐、磷酸盐和硫化物水溶解度的测定
配制标准0.1M的2,5-呋喃双亚胺胍盐酸盐水溶液，分别稀释至5×10 -5M、3×10 -5M、1×10 -5M、7×10 -6M、5×10 -6M，用浓度为5×10 -5M的2,5-呋喃双亚胺胍盐酸盐水溶液进行紫外光谱扫描(200-700nm)，得到最大吸收波长λ max＝346nm(如图10A所示)。在此波长下测定上述浓度梯度的吸光度，绘制标准曲线，得到曲线方程Y＝22.5663X-0.01329(如图10B所示)。
分别配制饱和碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)水溶液、饱和2,5-呋喃双亚胺胍硝酸盐水溶液、饱和2,5-呋喃双亚胺胍亚硫酸盐水溶液、饱和2,5-呋喃双亚胺胍盐酸盐水溶液、饱和2,5-呋喃双亚胺胍磷酸盐水溶液、饱和2,5-呋喃双亚胺胍硫化物水溶液，分别稀释100倍、1000倍、100倍、10000倍、100倍、100倍，测定紫外吸光度，代入方程y＝22.5663x-0.01329，得到其浓度分别为5.4(4)×10 -3M、3.3(2)×10 -2M、1.4(2)×10 -3M、0.74(6)M、3.1(3)×10 -3M、4.7(4)×10 -3M(如表3所示)。用pH计测定饱和碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)水溶液的pH为8.01(2)，已知HCO 3 -的pKa为10.32，计算得到饱和2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)水溶液的碳酸根离子的浓度[CO 3 2-]是2.6(2)×10 -5M。根据溶度积公式计算得碳酸2,5-呋喃双亚胺胍四水合物(FuBIGH 2(CO 3)(H 2O) 4)的溶度积为：
K sp＝[FuBIGH 2 2+][CO 3 2-]＝[5.4×10 -3][2.6×10 -5]＝1.4(4)×10 -7
表3各种FuBIG盐的溶解性
Figure PCTCN2018117144-appb-000007
以上实验表明，除盐酸盐外，2,5-呋喃双亚胺胍的阴离子盐都具有较小的水溶性，可以从水相中析出，证实2,5-呋喃双亚胺胍可作为一种阴离子沉淀剂应用。

Claims (10)

  1. 一种含有呋喃骨架的亚胺胍衍生物，其特征在于：是指2,5-呋喃双亚胺胍衍生物，包括2,5-呋喃双亚胺胍和2,5-呋喃双亚胺胍可接受的盐及其溶剂合物。
  2. 根据权利要求1所述的含有呋喃骨架的亚胺胍衍生物，其特征在于：所述的2,5-呋喃双亚胺胍具有以下结构式：
    Figure PCTCN2018117144-appb-100001
  3. 根据权利要求1所述的含有呋喃骨架的亚胺胍衍生物，其特征在于：所述2,5-呋喃双亚胺胍可接受的盐及其溶剂合物，包括其碳酸盐及其溶剂合物、亚硫酸盐及其溶剂合物、硫化物及其溶剂合物、盐酸盐及其溶剂合物、硫酸盐及其溶剂合物、硝酸盐及其溶剂合物、磷酸盐及其溶剂合物、次氯酸盐及其溶剂合物、高氯酸盐及其溶剂合物、重铬酸盐及其溶剂合物、高锰酸盐及其溶剂合物。
  4. 一种权利要求2所述2,5-呋喃双亚胺胍的制备方法，其特征在于包括下述步骤：以2,5-呋喃二甲醛为原料，与盐酸氨基胍在溶剂A中反应；反应完成后，将反应液在一定温度下静置，过滤，得到2,5-呋喃双亚胺胍盐酸盐；再经碱化，二次静置，得到2,5-呋喃双亚胺胍；所述2,5-呋喃二甲醛是以可再生生物质资源5-羟甲基糠醛为原料制备得到；所述2,5-呋喃二甲醛与盐酸氨基胍的摩尔比为1:1～1:3；所述2,5-呋喃双亚胺胍盐酸盐与碱的摩尔比为1:2～1:4；所述溶剂A是甲醇、乙醇、1,4-二氧六环或四氢呋喃；所述碱化，采用的碱是氢氧化钠、氢氧化钾、碳酸钠、碳酸钾或碳酸铯。
  5. 一种权利要求1所述的2,5-呋喃双亚胺胍衍生物作为酸性气体吸收剂的用途，其特征在于：在溶剂B中，2,5-呋喃双亚胺胍衍生物与酸性气体或含酸性气体的混合气体接触，形成沉淀析出，过滤，得到沉淀A，即含有2,5-呋喃双亚胺胍及酸性气体相关阴离子的盐，此盐具有很低的液相溶解性，将其加热至一定温度，可释放出酸性气体，并使2,5-呋喃双亚胺胍再生循环使用。
  6. 根据权利要求5所述的2,5-呋喃双亚胺胍衍生物作为酸性气体吸收剂的用途，其特征在于：所述酸性气体包括二氧化碳、二氧化硫、三氧化硫、二氧化氮、一氧化氮、一氧化二氮或硫化氢；所述含酸性气体的混合气体包括上述酸性气体之间以任意比例混合，以及一种或多种酸性气体与空气、氮气、氧气或惰性气体以任意比例混合；所述溶剂B是水、甲醇、乙醇、丙酮、四氢呋喃、乙腈、1,4-二氧六环、环丁砜、N-甲基吡咯烷酮、聚乙二醇二甲醚 或碳酸丙烯酯中的一种或一种以上混合物。
  7. 根据权利要求5所述的2,5-呋喃双亚胺胍衍生物作为酸性气体吸收剂的用途，其特征在于：所述2,5-呋喃双亚胺胍衍生物作为二氧化碳吸收剂，用于二氧化碳捕获、利用及封存。
  8. 一种权利要求1所述的2,5-呋喃双亚胺胍衍生物作为阴离子沉淀剂的用途，其特征在于：在溶剂B中，2,5-呋喃双亚胺胍衍生物与阴离子产生强的结合作用并形成沉淀析出；阴离子包括碳酸根、碳酸氢根、亚硫酸根、亚硫酸氢根、硫酸根、硫酸氢根、硝酸根、硫化氢根、磷酸根、磷酸氢根、磷酸二氢根、高氯酸根、次氯酸根、重铬酸根或高锰酸根。
  9. 一种碳酸2,5-呋喃双亚胺胍四水合物结晶，其特征在于：是权利要求1所述的2,5-呋喃双亚胺胍与二氧化碳及水形成的碳酸2,5-呋喃双亚胺胍四水合物结晶，以单晶X-射线衍射结构分析测得：三斜晶系，空间群为P-1，晶胞参数为
    Figure PCTCN2018117144-appb-100002
    Figure PCTCN2018117144-appb-100003
    α＝97.547(3)°，β＝111.174(3)°，γ＝112.709(4)°；
    Figure PCTCN2018117144-appb-100004
    密度＝1.484g/cm 3。
  10. 一种碳酸2,5-呋喃双亚胺胍四水合物的晶型，其特征在于：是权利要求1所述的2,5-呋喃双亚胺胍与二氧化碳及水形成的碳酸2,5-呋喃双亚胺胍四水合物的晶型，结晶以2θ角度和晶面间距(d值)表示的X-射线粉末衍射在约6.85(12.9)、7.87(11.2)、8.67(10.2)、13.48(6.6)、15.27(5.8)、15.87(5.6)、19.05(4.7)、19.77(4.5)、21.06(4.2)、24.45(3.6)、25.75(3.5)、27.75(3.5)、27.98(3.2)有特征峰。
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