CN109046255A - A kind of metal-organic framework desulfuration adsorbent and preparation method thereof - Google Patents
A kind of metal-organic framework desulfuration adsorbent and preparation method thereof Download PDFInfo
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- CN109046255A CN109046255A CN201811000721.7A CN201811000721A CN109046255A CN 109046255 A CN109046255 A CN 109046255A CN 201811000721 A CN201811000721 A CN 201811000721A CN 109046255 A CN109046255 A CN 109046255A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a kind of metal-organic framework desulfuration adsorbents and preparation method thereof, wherein the preparation method is as follows: (1) prepares two tooth organic ligands 3 of sulfur-bearing, 4- dimethyl bithiophene -2,5- dicarboxylic acids；(2) with Zn (NO3)2·6H2O, 3,4- dimethyl bithiophene -2,5- dicarboxylates and three tooth carboxylic acid H3BTB ligand is raw material, using one kettle way solvent-thermal process metal-organic framework desulfuration adsorbent, the process conditions of solvent-thermal process are as follows: be warming up to 85 DEG C in 1h, keep being cooled to 30 DEG C with the rate of 0.3 DEG C/min after 48h, colorless and transparent crystalline product is obtained by filtration.The invention has the beneficial effects that: (1) preparation method simple, easily-controllable, is suitble to industrially be mass produced；(2) desulfuration adsorbent made from is to 80% or more the organic sulfurs such as thioether, thiophenic sulfur average desulfurization degree.
Description
Technical field
The present invention relates to a kind of desulfuration adsorbents and preparation method thereof, and in particular to a kind of metal-organic framework desulfurization suction
Attached dose and preparation method thereof, belong to technical field of chemistry.
Background technique
Organic sulfur compound there are problems that will lead to forming acid rain and other atmospheric environments in fossil fuel, but also can make
Noble metal catalyst in some organic reactions is inactivated because of poisoning.How efficient desulfurization is carried out, and production clean fuel is always
It is urgent problem in Chemical Manufacture.Catalytic desulfurhydrogenation method (HDS) is most common desulfurization side in modern industrial production
Method.In addition, oxidation sweetening method (ODS), desulfurization by oxidation and extraction method (OEDS), adsorbs doctor treatment and biochemical de-sulfur method (BDS) is several
Plant other sulfur methods being being used.But catalytic desulfurhydrogenation method requires the item that high temperature and pressure is kept in several catalytic process
Part requirement, it is very high to chemical industry equipment requirement, and this method generally requires to consume high amount of hydrogen, while there is also have to some
The problems such as machine sulfide is selectively low greatly limits its application.In this case, exploitation operating condition is milder takes off
Concern of the sulphur method by more and more researchers.Currently, due to being provided simultaneously with, the property of can be recycled is strong and operating process is mild
The characteristics of, absorption doctor treatment becomes sulfur method very with market prospects.
But existing adsorbent is mostly to utilize simple hole suction-operated, adsorbent main body and organic sulfur compound guest molecule
Between have no interaction force, cause lower organic sulfur compound to remove ability.
It can be synthesized by the preceding modification of organic ligand due to pore structure and modify synthesis afterwards and be designed adjusting, MOFs is in gas
Body and liquid storage separation field are used widely.Yaghi seminar, Matzger seminar and Jhung seminar have studied
A series of adsorption capacity of MOFs materials to harmful substance, it was demonstrated that application of the MOFs in terms of organic sulfur compound removal may
Property.
Due to the presence of duct big in three-dimensional structure or cage structure, MOFs material usually has very big specific surface
Product, this feature are very crucial in terms of the adsorption applications of MOFs material.However, the three-dimensional framework material with bigger serface
Highly unstable, interpenetrating phenomenon frequent occurrence between skeleton, which prevent the presence of bigger serface feature.
Summary of the invention
It is led present invention aim to address common adsorbent to organic sulfur compound without interaction and due to structure interpenetrating
It is de- to provide a kind of higher metal-organic framework of absorption desulfuration efficiency for the problems such as metal-organic framework specific surface area of cause reduces
Sulfur absorbent and its simple, easily-controllable preparation method.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of preparation method of metal-organic framework desulfuration adsorbent, which comprises the following steps:
Step1: two tooth Carboxylic acid ligands of sulfur-bearing are prepared, wherein the substituent group in two thiphene rings of tooth Carboxylic acid ligand two is equal
For methyl.
Dry potassium carbonate and acetylacetone,2,4-pentanedione are added in a solvent, 1-2h is stirred at room temperature.Then the mixeding liquid temperature is protected
It holds in below freezing, addition carbon disulfide and bromoacetate.The reaction mixture first first reacts 2-3h in tepidarium, then
6-8h is reacted in hot bath.Reactant pours into the reaction mixture in cold water after being cooled to room temperature.It filters, washing is produced
Object.
Above-mentioned white crystalline solid product and potassium hydroxide are added in the mixed liquor of 200-400ml second alcohol and water.It will
Said mixture is heated to reflux 12-16h, then cools to room temperature.The ethyl alcohol in mixture is removed, obtained aqueous solution is with dilute
HCl is adjusted to acidity.It filters, obtains the solid of white, after being washed with deionized 3-5 times, be placed in a vacuum drying oven drying, i.e.,
For 3,4- dimethyl bithiophene -2,5- dicarboxylates.
Step2: the metal-organic framework desulfuration adsorbent preparation of sulfur-containing ligand
By zinc salt, 3,4- dimethyl bithiophene -2,5- dicarboxylates and the dissolution of three tooth Carboxylic acid ligands are in a solvent.It should
Mixture is moved into the reaction kettle of polytetrafluoroethylene (PTFE), and 40-60h is heated at 80-100 DEG C, is then slowly dropped to room temperature, is obtained
Colorless and transparent prism-shaped crystal removes mother liquor with the mode toppled over, and washing obtains metal-organic framework desulfuration adsorbent material
Material.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step1,
Used solvent is one of DMF, DMSO, methanol or ethyl alcohol.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step1,
The ratio between amount of substance of the potassium carbonate, acetylacetone,2,4-pentanedione, carbon disulfide and bromoacetate is 5:1:1:2-6:1:1:2.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step1,
The water temperature of warm water should be controlled at 40-50 DEG C, and the water temperature of hot water should be controlled at 80-90 DEG C.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step1,
Washing should at least carry out more than three times.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step1,
The ratio between amount of solid product and potassium hydroxide's substance is 1:4.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step1,
The ratio between volume is 1:1-3:1 both in the mixed liquor of second alcohol and water.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step1,
The concentration of dilute hydrochloric acid should be controlled in 2.0-3.0molL-1Between.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step1,
Solution is adjusted to acidity, pH value should be controlled in 2-3 or so.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step2,
The ratio between amount of substance of zinc salt, 3,4- dimethyl bithiophene -2,5- dicarboxylates and three tooth Carboxylic acid ligand threes is 4:1:1-
7:1:1。
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step2,
The solvent is that N, N- diethylformamide, and dosage are 5ml.
A kind of preparation method of metal-organic framework desulfuration adsorbent material above-mentioned, which is characterized in that in Step2,
The method of washing is to be cleaned more than three times with dry DMF.
The invention has the beneficial effects that:
(1) by introducing methyl functional group on organic ligand, so that increasing methyl function base on the inner surface in hole
Group, the presence of these groups will increase the interaction force between skeleton subject and object molecule, and then effectively help to be promoted
Removal efficiency of the skeleton to organic sulfur compound.
(2) by introducing Ligands H3BTB, Successful utilization mixed ligand strategy, has constructed the porous of non-interpenetrating structure
MOFs material, the MOFs material obtained in this way not only have the structure of stable non-interpenetrating, but also possess and relatively large compare table
Area.Effective help is promoted into skeleton to the adsorption capacity of organic sulfur compound.
(3) preparation method of the invention is simple, easily-controllable, is suitble to industrially be mass produced.
Detailed description of the invention
The photo of the monocrystalline of product 1 under an optical microscope obtained by Fig. 1 embodiment 1；
Fig. 2 is thermogravimetric (TGA) curve graph of product 1 obtained by embodiment 1；
Fig. 3 is the IR figure of product 1 obtained by embodiment 1；
Fig. 4 is the structural schematic diagram of product 1 obtained by embodiment 1, the I contained in (a) structure, II, tri- kinds of caged of III
Structure, (b) topological diagram of product 1 obtained by embodiment 1, (c) the tile figure of product 1 obtained by embodiment 1；
Fig. 5 is the XRD diagram of product 1 obtained by embodiment 1；
Fig. 6 (a) is the N of product 1 obtained by embodiment 12Adsorption/desorption isothermal curve figure；
Fig. 6 (b) is the graph of pore diameter distribution of product 1 obtained by embodiment 1；
Fig. 7 (a) is the absorption desulfurization curve graph (BT) of product 1 obtained by embodiment 1；
Fig. 7 (b) is the absorption desulfurization curve graph (DBT) of product 1 obtained by embodiment 1；
Fig. 8 is the N after the absorption of product 1 obtained by embodiment 1 BT and DBT2Adsorption/desorption isothermal curve figure；Fig. 9 (a) is
The absorption desulfurization curve graph (BT) of product 2,3 obtained by embodiment 2,3；
Fig. 9 (b) is the absorption desulfurization curve graph (DBT) of product 2,3 obtained by embodiment 2,3；
Figure 10 (a) is the N after the absorption of product 2 obtained by embodiment 2 BT and DBT2Adsorption/desorption isothermal curve figure；
Figure 10 (b) is the N after the absorption of product 3 obtained by embodiment 3 BT and DBT2Adsorption/desorption isothermal curve figure.
Specific embodiment
Specific introduce is made to the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1:
Step 1: the synthesis of sulfur-containing ligand
(1) synthesis of 3,4- dimethyl bithiophene -2,5- dicarboxylic ester
Weigh 69.0g (0.5mol) potassium carbonate (K2CO3) and 10.0g (0.1mol) acetylacetone,2,4-pentanedione be added to 100mL DMF
In, 1-2h is stirred at room temperature.6.0mL (0.1mol) carbon disulfide is measured, 0 DEG C or less is maintained the temperature at and is added to above-mentioned reactant
0.5h stirs in system.22.0ml (0.2mol) bromoacetate is measured, 0 DEG C or less is maintained the temperature at and is added to above-mentioned reaction system.
This reaction system is reacted into 2-3h under conditions of 40-50 DEG C, is warming up to 80-90 DEG C the reaction was continued reaction 6-8h.It is cooling, by this
Reaction mixture pours into 300mL water.It filters, washing.Obtain product 3,4- dimethyl bithiophene -2,5- dicarboxylic ester, through counting
It calculates: yield 92%.
(2) synthesis of 3,4- dimethyl bithiophene -2,5- dicarboxylic acids
It weighs the above-mentioned solid of 4.0g (0.015mol) and 3.2g (0.06mol) KOH is added to the mixing of 200ml second alcohol and water
In liquid (1:1).It is cooled to room temperature after this system is heated to reflux 12-16h.Heat the ethyl alcohol in removing system, obtained aqueous solution
Use 1.0-3.0molL-1It is 2-3 that dilute HCl solution, which is adjusted to pH,.It filters, obtains the solid of white, as 3,4- dimethyl and thiophene
Pheno -2,5- dicarboxylic acids (H2DMTDC), it is washed with deionized, is dried in vacuo.It is computed: yield 92%.
Step 2: one kettle way solvent-thermal process metal-organic framework desulfuration adsorbent
Weigh 0.11g Zn (NO3)2·6H2O(0.37mmol),0.012g H2DMTDC (0.050mmol) and 0.022g
H3BTB (0.050mmol) is dissolved in 5ml DEF.40-60h is heated at 80-100 DEG C, is subsequently reduced to room temperature, is obtained colourless
Transparent prism-shaped crystal, removes mother liquor, washing.It is computed: yield 68%.
We have carried out Structural Identification to colourless transparent crystal product (being denoted as 1) obtained by embodiment 1.
Pass through mixed ligand and Zn (NO3)2·6H2The synthetic method for the solvent heat that O is carried out, we have obtained complete pure phase
Clear crystal 1.The photo of its monocrystalline under an optical microscope is as shown in Figure 1, the photo of crystal proves crystal knot under microscope
Crystalline substance is very high.
Its single crystal data is measured by single crystal X-ray diffraction, molecular formula C46H26O13.25S2Zn4, molecular weight 1116.15,1
Crystallization is in tetragonal space group P63/ m, α=90.00 °, β=
90.00 °, γ=120.00 °.Its infrared and thermogravimetric spectrogram is as shown in Figures 2 and 3.In infrared spectrum it is strong, in, weak feature
Peak is IR (cm-1): 3442.76 (strong), 1555.77 (in), 1500.31 (in), 1390.00 (strong), 1255.12 (strong),
1062.53 (weak), 1015.88 (weak), 859.85 (weak), 782.17 (in).
The molecular formula that 1 is determined by elemental analysis and thermogravimetric analysis (TGA) is Zn4O(DMTDC)(BTB)4/3。
Fig. 4 is the structural schematic diagram of product 1 obtained by embodiment 1.Structural analysis shows that there are two micropore cages in 1
(Cages I and Cages III) and mesoporous cage (Cage II).Pass through the calculating of PLATON/SQUEEZE, 1 institute of embodiment
The porosity of product 1 obtained is 82.42%.
Fig. 5 is the XRD diagram of product 1 obtained by embodiment 1.Powder x-ray diffraction data is research shows that 1 institute of embodiment
1 diffraction maximum of product obtained and 1 diffraction maximum of simulation are coincide very good.Prove that the phase of crystal is very pure.
Fig. 6 (a) is the N of product 1 obtained by embodiment 12Adsorption/desorption isothermal curve.Fig. 6 (b) is that embodiment 1 is made
The graph of pore diameter distribution of the product 1 obtained.
PXRD figure and N2Adsorption/desorption isothermal curve proves that the hole characteristic of product 1 obtained by embodiment 1 is protected after activation
It holds intact.
It is learnt by adsorption of nitrogen gas data calculating, the BET specific surface area of product 1 obtained by embodiment 1 is 3648m2/ g,
And corresponding Langmuir specific surface area is 5640m2/g.By theoretical calculation, we have obtained product obtained by embodiment 1
1 pore-size distribution, wherein the main aperture size integrated distribution of product 1 obtained by COMPOUNDS EXAMPLE 1 exists
The result of identification: 1 crystal phase purity is high of product obtained by embodiment 1, crystallinity is high, and inside configuration has
Very big specific surface area, pore-size distribution are relatively uniform；Uniform methyl functional group of arranging, structure height have inside duct
Sequence, will generate interaction to guest molecule, and product 1 is good adsorbent material.Step 3: absorption desulfurization test
Metal-organic framework desulfuration adsorbent of the invention is mainly used in gasoline, diesel desulfuration field.Adsorption experiment choosing
It selects and is carried out in the isooctane solution of benzothiophene (BT) and dibenzothiophenes (DBT) that concentration is 3500ppmw S or so, point
Analysing selection of time is 12 hours.Product 1 obtained by embodiment 1 is shown to the very high adsorption capacity of organic sulfur compound.
Under 298K, 0.005g crystal is weighed, is added in the isooctane solution of BT and DBT that 1ml contains various concentration.So
Afterwards, vial is placed on vibrator with 150rev min-1Speed vibrate 12 hours.This adsorption process is supervised by UV/Vis spectrum
It surveys, carries out desulfurization concentration analysis with chromatography of gases GC-FID.
Metal-organic framework desulfuration adsorbent obtained by embodiment 1 adsorbs desulfurization test curve such as Fig. 7, Fig. 8.
Product 1 obtained by embodiment 1 is as follows to the adsorption capacity of organic sulfur compound, and Fig. 7 (a) is to the adsorption capacity of BT
45g S/kg MOF (1500ppmw S), corresponding 189g BT/kg MOF (1500ppmw S).Fig. 7 (b) implements DBT
The adsorption capacity of product 1 obtained by example 1 is 69g S/kg MOF (1500ppmw S), corresponds to 395g DBT/kg MOF
(1500ppmw S)。
To prove that BT molecule and DBT molecule do enter into duct, we are to having adsorbed benzothiophene and dibenzo
The solid crystals BT@1 and DBT@1 of thiophene have carried out nitrogen adsorption test.
Under 77K, metal-organic framework desulfuration adsorbent obtained by embodiment 1, the N of the sample after adsorbing desulfurization2It inhales
Attached curve such as Fig. 8.
As schemed to have adsorbed the BET specific surface area of product 1 obtained by the embodiment 1 of BT and DBT molecule and Langmuir ratio
Surface area has a degree of decline.Prove that BT and DBT molecule does enter into the duct of product 1 obtained by embodiment 1
In the middle.
It should be noted that the above embodiments do not limit the invention in any form, it is all to use equivalent replacement or equivalent change
The mode changed technical solution obtained, falls within the scope of protection of the present invention.
Embodiment 2
Weigh 69.0g (0.5mol) potassium carbonate (K2CO3) and 16.2g (0.1mol) 1-phenylbutane-1,3-dione
It is added in 100mL DMF, 1-2h is stirred at room temperature.6.0mL (0.1mol) carbon disulfide is measured, 0 DEG C or less is maintained the temperature at and adds
Enter to above-mentioned reaction system, stirs 0.5h.22.0ml (0.2mol) bromoacetate is measured, 0 DEG C or less addition is maintained the temperature at
To above-mentioned reaction system.The reaction mixture first reacts 2-3h under conditions of 40-50 DEG C, and being warming up to 80-90 DEG C, the reaction was continued
React 6-8h.It is cooling, which is poured into 300mL water.It filters, washing.Obtain product diethyl3-methyl-
4-phenylthieno [2,3-b] thiophene-2,5-dicarboxylate, is computed: yield 80%.
It weighs the above-mentioned solid of 4.0g (0.015mol) and 3.2g (0.06mol) KOH is added to the mixing of 200ml second alcohol and water
In liquid (1:1).It is cooled to room temperature after this system is heated to reflux 12-16h.Heat the ethyl alcohol in removing system, obtained aqueous solution
Use 1.0-3.0molL-1It is 2-3 that dilute HCl solution, which is adjusted to pH,.It filters, obtains the solid of white, as 3-methyl-4-
phenylthieno[2,3-b]thiophene-2,5-dicarboxylic acid(H2MPTDC), it is washed with deionized, very
Sky is dry.It is computed: yield 88%.
Weigh 0.11g Zn (NO3)2·6H2O(0.37mmol),0.0076g H2MPTDC (0.025mmol) and 0.0109g
H3BTB (0.025mmol) is dissolved in 5ml DEF.40-60h is heated at 80-100 DEG C, is subsequently reduced to room temperature, is obtained colourless
Transparent bulk crystals remove mother liquor, washing.It is computed: yield 51%.
We have also carried out Structural Identification to crystalline product 2 made from embodiment 2, and structure is by proton magnetic1H NMR test
As a result it is determined with after the Structure Comparison of product 1 made from embodiment 1, crystallogram, IR figure, TGA figure, caged under microscope
Structure chart, XRD diagram, N2The phase of adsorption/desorption curve, pore size distribution curve and product colourless transparent crystal 1 made from embodiment 1
Map is answered to be consistent substantially.This explanation: the change of ligand function group does not have an impact crystal phase state purity, crystallinity etc.,
Very big specific surface area is all had, pore-size distribution is uniform；Uniform functional group of arranging, structure height are orderly inside duct.
We have also carried out absorption desulfurization test to product 2 made from embodiment 2.Test result: embodiment 2 is obtained to be produced
It is adsorbed shown in desulfurization test curve such as Fig. 9 (a) object 2, the crystal N after absorption organic sulfur compound2Adsorption curve such as Figure 10 (a) institute
Show, shows the adsorbance and adsorption efficiency to organic sulfur compound superelevation.
Embodiment 3
Weigh 69.0g (0.5mol) potassium carbonate (K2CO3) and 22.4g (0.1mol) 1,3-diphenylpropane-1,3-
Dione is added in 100mL DMF and is added, and 1-2h is stirred at room temperature.6.0mL (0.1mol) carbon disulfide is measured, temperature drop is kept
It is added to above-mentioned reaction system at 0 DEG C or less, stirs 0.5h.22.0ml (0.2mol) bromoacetate is measured, temperature drop is kept
Above-mentioned reaction system is added at 0 DEG C or less.The reaction mixture first reacts 2-3 hours under conditions of 40-50 DEG C, is warming up to
80-90 DEG C the reaction was continued reaction 6-8 hours.It is cooling, which is poured into 300mL water.It filters, washing.It is produced
Object diethyl 3,4-diphenylthieno [2,3-b] thiophene-2,5-dicarboxylate, be computed: yield is
60%.
It weighs 4.0g (0.015mol) above-mentioned solid and 3.2g (0.06mol) KOH is added to the mixing of 200ml second alcohol and water
In liquid (1:1).It is cooled to room temperature after this system is heated to reflux 12-16h.Heat the ethyl alcohol in removing system, obtained aqueous solution
Use 1.0-3.0molL-1It is 2-3 that dilute HCl solution, which is adjusted to pH,.Filter, obtain white solid, as 3,4-
diphenylthieno[2,3-b]thiophene-2,5-dicarboxylic acid(H2DPTDC), it is washed with deionized,
Vacuum drying.It is computed: yield 80%.
Weigh 0.11g Zn (NO3)2·6H2O(0.37mmol),0.024g H2DPTDC (0.068mmol) and 0.014g
H3BTB (0.034mmol) is dissolved in 5ml DEF.40-60h is heated at 80-100 DEG C, is subsequently reduced to room temperature, is obtained colourless
Transparent bulk crystals remove mother liquor, washing.It is computed: yield 56%.
We have also carried out Structural Identification to crystalline product 3 made from embodiment 3, and structure is by proton magnetic1H NMR test
As a result it is determined with after the Structure Comparison of product 1 made from embodiment 1, crystallogram, IR figure, TGA figure, caged under microscope
Structure chart, XRD diagram, N2The phase of adsorption/desorption curve, pore size distribution curve and product colourless transparent crystal 1 made from embodiment 1
Map is answered to be consistent substantially.This explanation: the change of ligand function group does not have an impact crystal phase state purity, crystallinity etc.,
Very big specific surface area is all had, pore-size distribution is uniform；Uniform functional group of arranging, structure height are orderly inside duct.
We have also carried out absorption desulfurization test to product 3 made from embodiment 3.Test result: embodiment 3 is obtained to be produced
It is adsorbed shown in desulfurization test curve such as Fig. 9 (b) object 3, the crystal N after absorption organic sulfur compound2Adsorption curve such as Figure 10 (b) institute
Show, shows the adsorbance and adsorption efficiency to organic sulfur compound superelevation.
Claims (6)
1. a kind of preparation method of metal-organic framework desulfuration adsorbent, which comprises the following steps:
Step1: two tooth Carboxylic acid ligand of sulfur-bearing preparation, wherein the substituent group in two thiphene rings of tooth Carboxylic acid ligand two is methyl.
Step2: with zinc salt, two tooth Carboxylic acid ligand of sulfur-bearing and H3BTB ligand is primary raw material, using one kettle way solvent-thermal process gold
Category-organic backbone desulfuration adsorbent.
2. a kind of preparation method of metal-organic framework desulfuration adsorbent material according to claim 1, feature exist
In, in Step1, the two teeth Carboxylic acid ligand the preparation method comprises the following steps:
(1) dry potassium carbonate and acetylacetone,2,4-pentanedione are added in a solvent, 1-2h is stirred at room temperature.Then the mixeding liquid temperature is kept
In below freezing, addition carbon disulfide and bromoacetate；The potassium carbonate, acetylacetone,2,4-pentanedione, carbon disulfide and bromoacetate
The ratio between four amount of substance is 5:1:1:2-6:1:1:2；
(2) reaction mixture first reacts 2-3h in 40-50 DEG C of tepidarium, then reacts 6-8h in 80-90 DEG C of hot bath.
Reactant pours into the reaction mixture in cold water after being cooled to room temperature.It filters, washing obtains product；
It (3) is that 1:4 is added to 200-400ml second according to the ratio between amount of substance by above-mentioned white crystalline solid product and potassium hydroxide
In the mixed liquor of alcohol and water.Said mixture is heated to reflux 12-16h, is then cooled to room temperature；
(4) ethyl alcohol in mixture, obtained aqueous solution 1.0-3.0molL are removed-1Dilute HCl be adjusted to pH=2-3.It takes out
Filter obtains the solid of white, after being washed with deionized 3-5 times, is placed in a vacuum drying oven drying, as 3,4- dimethyl is simultaneously
Thiophene -2,5- dicarboxylates.
3. a kind of preparation method of metal-organic framework desulfuration adsorbent material according to claim 1, feature exist
In, in Step2, zinc salt, two tooth Carboxylic acid ligand of sulfur-bearing and H3The ratio between amount of substance of BTB ligand three is 4:1:1-7:1:1.
4. a kind of preparation method of metal-organic framework desulfuration adsorbent material according to claim 1, feature exist
In, in Step2, the process conditions of one kettle way solvent-thermal process are as follows: at 80-100 DEG C heat 40-60h after with 1.5-2 DEG C/
The rate of min is cooled to 20-25 DEG C, and washing obtains colorless and transparent prism-shaped crystal after drying.
5. a kind of preparation method of metal-organic framework desulfuration adsorbent material according to claim 2, feature exist
In in Step1, used solvent is one of DMF, DMSO, methanol or ethyl alcohol.
6. a kind of preparation method of metal-organic framework desulfuration adsorbent material according to claim 2, feature exist
In in Step1, the ratio between volume is 1:1-3:1 both in the mixed liquor of second alcohol and water.
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