CN103084212B - Supported vanadium-substituted polyacid desulfurization catalyst porous nanocrystal and preparation method thereof - Google Patents
Supported vanadium-substituted polyacid desulfurization catalyst porous nanocrystal and preparation method thereof Download PDFInfo
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- CN103084212B CN103084212B CN201210290016.1A CN201210290016A CN103084212B CN 103084212 B CN103084212 B CN 103084212B CN 201210290016 A CN201210290016 A CN 201210290016A CN 103084212 B CN103084212 B CN 103084212B
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Abstract
The invention provides a preparation method of a supported vanadium-substituted Keggin type polyacid desulfurization catalyst porous nanocrystal. The catalyst is formed by using a three-dimensional porous main body framework constituted by copper and trimesic acid through a coordination bond to support vanadium-substituted Keggin type molybdatophosphoric acid. Polyacid is orderly arranged in the main body framework in an object form, and the supporting amount is above 54%. The nanocrystal catalyst can be synthesized by a room-temperature solid phase or room-temperature liquid phase method and be stably dispersed in an oil phase. Under mild conditions, molecular oxygen is taken as an oxidant, and the nanocrystal can efficiently realize catalytic oxidation of aromatic sulfides in fuel oil and further realize deep desulfurization. The catalyst can be recovered by centrifugal operation and be reused mainly times after drying treatment. The preparation method of the polyacid nanocrystal desulfurization catalyst, provided by the invention, is simple, can effectively solve the technical difficult problems of immobilization, separation, recovery, reuse and stable dispersion in the oil phase of the polyacid catalyst, and is suitable for industrial production.
Description
Technical field
[0001] the invention belongs to catalysis material preparing technical field, relate to the preparation method that a kind of loaded vanadium replaces polyacid desulphurization catalyst porous nanocrystalline.
Background technology
[0002] polyoxometallate (polyoxometalates is abbreviated as POMs), also claims polyacid compound, by early transition metal (Mo, W, V, Nb, Ta etc.) connect the class forming and have inorganic metal-oxygen cluster compound of nano-scale by oxygen.Because it has stronger acidity and reversible redox characteristic, receive much attention at catalytic field.Mainly that general formula is [XM as the polyoxometallate of catalyst at present
12o
40]
n-keggin type heteropoly compound, wherein X is mainly P, Si, Ge, As etc., M is mainly Mo, W etc.Because Keggin type polyacid compound has high, synthetic simple, cheap, the advantages of environment protection of stability concurrently, both can show superpower acidity, also can show reversible polyelectron redox characteristic.Therefore, they can be used as acid catalyst, oxidation catalyst or bifunctional catalyst (acid catalysis and oxidation catalysis), are widely used for the polytype chemical reaction of catalysis.And its power acid and oxidisability, can, when holding structure is constant, regulate by the chemical composition that changes polyacid.The Keggin type polyacid of Transition metal substituted and classical tungsten system and molybdenum are that polyacid is compared and had higher oxidation potential, and in showing compared with strong oxidizing property, its reduction-state is easier to be again oxidized by oxygen under gentle condition.Therefore, the Keggin type polyacid of Transition metal substituted is widely studied as the application of aerobic oxidation agent.
Petroleum sweetening is an important subject of PETROLEUM PROCESSING industry.Taking molecular oxygen as oxidant, under gentle condition, realizing deep desulfuration is the target that people pursue for a long time always.The Keggin type molybdenum phosphorus polyacid that vanadium replaces is one of the catalyst that can realize oxidation desulfur reaction under the condition of molecular oxygen as oxidant few in number of report at present, does is but the problem facing how the polyacid catalyst of polarity to be incorporated in nonpolar oil phase (oil) and to contact and react with reactant? current, the representativeness strategy that polyacid is introduced to oil phase be by polyoxoanion and the organic ammonium cationic surfactant with long alkyl chain by electrostatic force combination, make parental type polyacid catalyst.In this type of catalyst, polyacid is wrapped in centre by the lipophile organic ammonium cation that has long alkyl chain, thereby polyacid can be disperseed preferably in oil phase or microemulsion system, brings into play its catalytic performance.The people such as Li Can (Chem. Commun., 2007,150 – 152) use [C
18h
37n (CH
3)
3]
+as lipophile cationic surfactant groups, by [PV
2mo
10o
40]
5-be wrapped in wherein, made a kind of amphiphilic desulphurization catalyst.This catalyst and acetonitrile, decahydronaphthalene are mixed to form to microemulsion system by fixed proportion, can the dibenzothiophenes in diesel oil analogies decahydronaphthalene be oxidized to sulfone or/and sulfoxide under as oxidant condition at molecular oxygen, finally by using polar solvent extract, remove sulfone wherein or/and sulfoxide, realize the deep oxidation desulfurization of fuel oil.But there is following problem in this catalyst:
1, " micro emulsion " reaction system is to mix by a certain percentage spontaneous formation by water, oil phase, surfactant with cosurfactant.Each component ratio determines, any variation all can cause the unstable of system, therefore " micro emulsion " system be easy to because of the minor alteration of reaction condition destroyed.In addition, catalyst is to form by the electrostatic interaction of zwitterion, active force a little less than, polyacid catalytic center easily with the disengaging of surfactant cation, and lose catalytic activity.Organic amine cation after simultaneously departing from polyacid catalytic center can be dissolved in contaminated product in oil phase.
2, the long alkyl chain organic ammonium cation that is wrapped in polyacid surface can produce larger sterically hindered, hinders reaction substrate and contacts with polyacid catalytic center, can not give full play to the catalytic activity of polyacid.
3, the separation of catalyst is reclaimed and need to first be carried out " breakdown of emulsion " operation, and removal process is loaded down with trivial details.Because the polyacid catalyst stability of this surfactant parcel is poor, in the catalyst reclaiming, can be mixed with the polyacid splitting away off simultaneously, need further to process rear and can be recycled.
Summary of the invention
One of object of the present invention is in oil phase, to disperse, separate, reclaim and recycle the technical barriers such as difficulty for solving polyacid catalyst, the Keggin type molybdenum phosphorus polyacid desulphurization catalyst porous nanocrystalline that provides a kind of loaded vanadium to replace.Here the Keggin type molybdophosphate that vanadium replaces comprises that vanadium one replaces, two replacements and three replace molybdophosphates, and its chemical formula is respectively H
4pVMo
11o
40, H
5pV
2mo
10o
40and H
6pV
3mo
9o
40.
Two of object of the present invention is to provide a kind of preparation method of Keggin type molybdenum phosphorus polyacid desulphurization catalyst porous nanocrystalline of loaded vanadium replacement.
Design philosophy of the present invention is as follows:
1, by polyacid catalyst loading to the three-dimensional porous metal-organic framework of being constructed by metallic copper and trimesic acid, in the main body frame of MOF, prepare loaded polyacid catalyst.
2, utilize the porous of main body frame, realize the ordered arrangement (seeing accompanying drawing 1) of polyacid catalyst.
3,, because the organic ligand trimesic acid of main body frame has hydrophobic phenyl ring, melt mutually because of similar blind date to oil.When this catalyst size controls to enough littlely while reaching nanometer, can stably be dispersed in oil phase, do not reunite.Meanwhile, catalyst size is less, and specific area is larger, and surface catalysis active site is just more, and the duct of catalyst is also shorter, and reaction substrate diffusion is more rapid, shows higher catalytic activity.
The crystal structure information of this class catalyst obtains by the following method:
Obtain metal organic frame by Hydrothermal Synthesis and support the crystal that vanadium replaces Keggin type polyacid.Here with the dibasic H of vanadium
5pV
2mo
10o
40it is as follows that polyacid is that example is described experimental technique: 0.24 g Cu (NO
3)
23H
2o (1mmol) and 0.2 g H
5pV
2mo
10o
40be dissolved in 10 ml deionized water.Add successively 0.21 g 1,3,5-trimesic acid (H
3tMA, 1 mmol), pH is transferred to 2-3 with TMAH.At room temperature stir 30 minutes.This mixture is packed in the autoclave of teflon lined, under 180 oC, heat after 24 hours with 10 DEG C of h
-1speed drop to room temperature, obtain green bulk crystals.Product is passed through to Single Crystal X-ray diffraction, powder x-ray diffraction (PXRD), infrared (IR), elementary analysis, N
2adsorption experiment and thermogravimetric analysis characterize, and have obtained the accurate information about crystal structure, and concrete outcome is described below:
The molecular formula of crystal is Cu
12(TMA)
8h
3pV
2mo
10o
40(C
4h
12n)
226H
2o.In its structure, main body frame is Cu
3(TMA)
2, polyanionic H3PV
2mo
10o
40 2-for object.Main body frame Cu
3(TMA)
2in contain three kinds of holes, see accompanying drawing 1 with hole A, hole B and hole C(respectively) represent, between hole, communicate with each other.Its mesopore A is occupied by polyacid, and residue hole is formed through three-dimensional duct mutually, makes whole crystal structure have the attribute of micropore.Some removable guest molecules in duct, are also held, as tetramethyl amine cation [C
4h
12n]
+and water.
The above-mentioned metal organic frame that obtains supports the crystal drying processing that vanadium replaces Keggin type polyacid and loses the crystallization water and tetramethyl amine, and the structure of main body frame and polyacid is constant, and the available following general formula of its composition represents: Cu
12(TMA)
8h
n+3pV
nmo
12-no
40, in formula, n gets 1,2,3, the english abbreviation that TMA is trimesic acid.
Loaded vanadium provided by the invention replaces polyacid desulphurization catalyst porous nanocrystalline and can prepare by the following method:
(1) room temperature liquid phase is synthetic:
The Keggin type molybdophosphate that the soluble copper salt that is 3 ~ 4:1 by 1 gram of amount of substance ratio and vanadium replace is dissolved in 5 ~ 20 ml waters, and pH is adjusted to 2 ~ 4.The trimesic acid that the ratio that takes the amount of substance of the Keggin type molybdophosphate replacing with vanadium is 1 ~ 2:1, is dissolved in 5 ~ 20 milliliters of ethanol.Under agitation, the ethanolic solution of trimesic acid is added drop-wise in the aqueous solution of polyacid and mantoquita, in solution, engender green precipitate, centrifugation, washing, oven dry precipitation, finally obtain loaded vanadium and replace Keggin type molybdophosphate desulphurization catalyst porous nanocrystalline.
(2) Room Temperature Solid State is synthetic:
The Keggin type molybdophosphate that the soluble copper salt that is 3 ~ 4:1 by 1 gram of amount of substance ratio and vanadium replace is dissolved in 5 ~ 20 ml waters, and pH is adjusted to 2 ~ 4, and solvent evaporated obtains the mix powder of polyacid and mantoquita.The trimesic acid that the ratio that takes the amount of substance of the Keggin type molybdophosphate replacing with vanadium is 1 ~ 2:1, in agate mortar, mix and grind with above-mentioned powder, it is green that reactant color gradually becomes, water and ethanol is supersound washing post-drying product for several times respectively, finally obtains loaded vanadium and replaces Keggin type molybdophosphate desulphurization catalyst porous nanocrystalline.
In above-mentioned preparation method, the amount that changes in proportion reactant can increase or reduce catalyst yield, and above-mentioned soluble copper salt is copper nitrate, Schweinfurt green, copper chloride, copper sulphate etc.; The Keggin type molybdophosphate that vanadium replaces is: H
4pVMo
11o
40, H
5pV
2mo
10o
40and H
6pV
3mo
9o
40.In the time that the Keggin type molybdophosphate of vanadium replacement is respectively a replacement, two replacements and three replacement vanadium, the chemical formula that the loaded vanadium making replaces Keggin type molybdophosphate desulphurization catalyst porous nanocrystalline is respectively: Cu
12(TMA)
8h
4pVMo
11o
40, Cu
12(TMA)
8h
5pV
2mo
10o
40and Cu
12(TMA)
8h
6pV
3mo
9o
40.
The structure that the loaded vanadium that said method makes replaces Keggin type molybdophosphate desulphurization catalyst porous nanocrystalline characterizes by X-ray powder diffraction (PXRD is shown in accompanying drawing 2) and infrared spectrum (IR is shown in accompanying drawing 3).Can find by contrast, in PXRD and IR spectrogram, the synthetic crystal of hydrothermal method is all consistent with nanocrystalline peak position and peak intensity, and this has proved to have identical structure with the synthetic nanocrystalline and synthetic crystal of hydrothermal method of said method.Simultaneously, can determine by scanning electron microscope image, nanocrystalline pattern, size homogeneous that said method makes, the synthetic nanocrystalline particle diameter of Room Temperature Solid State (is shown in accompanying drawing 4) between 50 ~ 200 nanometers, the synthetic nanocrystalline particle diameter of room temperature liquid phase (is shown in accompanying drawing 5) between 400 ~ 900 nanometers.Nitrogen adsorption experiment has confirmed this nanocrystalline porous (seeing accompanying drawing 7), and its BET specific area is about 500 m
2g
-1.
Loaded vanadium provided by the invention replaces Keggin type molybdophosphate porous nanocrystalline catalyst and is applied in oxidative desulfurization of fuel oils, can under temperate condition, use oxygen as oxidant, aromatic series sulfide in fuel oil is converted into corresponding sulfone and/or sulfoxide, uses polar solvent extract product sulfone and/or sulfoxide can obtain deep desulfuration oil product.
Above-mentioned aromatic series sulfide is thiophene, benzothiophene, dibenzothiophenes, dimethyl Dibenzothiophene etc., and polar solvent is selected methyl alcohol, ethanol, formic acid, acetic acid, acetonitrile etc., and conversion ratio is monitored by chromatography of gases.
The loaded vanadium providing in the present invention replaces polyacid porous nanocrystalline desulphurization catalyst and has following characteristics:
1, loaded vanadium replacement polyacid desulphurization catalyst porous nanocrystalline is by stable Cu
3(TMA)
2porous framework parcel polyacid object forms, and polyacid object is at Cu
3(TMA)
2ordered arrangement in main body frame.Supporting the porous of main body frame after polyacid still keeps.Catalyst forms, structure is determined, the loading of polyacid catalyst is up to more than 54%.
2, loaded vanadium replace the nanocrystalline desulphurization catalyst of polyacid can stable dispersion in oil phase, desulphurization reaction can directly be carried out in oil phase, unsettled without constructing " micro emulsion " system.
3, catalyst can be separated completely, be reclaimed by simple centrifugally operated, and not polluted product has been avoided the loaded down with trivial details propagation of " breakdown of emulsion ", and drying is processed reusable, still can keep good catalytic activity after being repeatedly used.
4, catalyst preparation method is simple, and in manufacturing process, no coupling product generates, and separating-purifying is convenient, is conducive to industrial production.
Brief description of the drawings
Fig. 1 is the crystal structure that loaded vanadium replaces polyacid porous nanocrystalline.Cu
3(TMA)
2there are three kinds of hole: A, B and C.Be wrapped in the A of hole anion selectivity.Hole A and B, B and C connect.
Fig. 2 is the X-ray powder diffraction figure that loaded vanadium replaces polyacid porous nanocrystalline: a) according to Single Crystal X-ray diffraction data, with the XRD of Mercury software simulation; B) the X-ray powder diffraction figure of the crystal of Hydrothermal Synthesis; C) the synthetic nanocrystalline X-ray powder diffraction figure of room temperature liquid phase; D) the synthetic nanocrystalline X-ray powder diffraction figure of Room Temperature Solid State.
The loaded vanadium of Fig. 3 replaces the infrared spectrogram of polyacid porous nanocrystalline: a) infrared spectrogram of the crystal of Hydrothermal Synthesis; B) the synthetic nanocrystalline infrared spectrogram of room temperature liquid phase; C) the synthetic nanocrystalline infrared spectrogram of Room Temperature Solid State.
Fig. 4 is the scanning electron microscope (SEM) photograph that the synthetic loaded vanadium of Room Temperature Solid State replaces polyacid porous nanocrystalline.
Fig. 5 is the scanning electron microscope (SEM) photograph that the synthetic loaded vanadium of room temperature liquid phase replaces polyacid porous nanocrystalline.
Fig. 6 is the conversion ratio curve over time of dibenzothiophenes in simulation diesel oil (decahydronaphthalene).
Fig. 7 is that loaded vanadium replaces nitrogen adsorption isotherm under the 77K condition of polyacid porous nanocrystalline.
Detailed description of the invention
In order to further illustrate the present invention, enumerate following embodiment, but it does not limit the defined invention scope of each accessory claim.
Specific embodiment 1:Cu
12(TMA)
8h
5pV
2mo
10o
40room Temperature Solid State synthetic
Get 0.24 gram of Cu (NO
3)
23H
2o and 0.5 gram of H
5pV
2mo
10o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 2:Cu
12(TMA)
8h
5pV
2mo
10o
40room Temperature Solid State synthetic
Get 0.2 gram of Cu (CH
3cOO)
2h
2o and 0.5 gram of H
5pV
2mo
10o
40be dissolved in 10 ml deionized water, pH be adjusted to 2 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 3:Cu
12(TMA)
8h
5pV
2mo
10o
40room Temperature Solid State synthetic
Get 0.34 gram of CuCl
22H
2o and 1 gram of H
5pV
2mo
10o
40be dissolved in 20 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.42 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 4:Cu
12(TMA)
8h
5pV
2mo
10o
40room Temperature Solid State synthetic
Get 0.25 gram of CuSO
45H
2o and 0.5 gram of H
5pV
2mo
10o
40be dissolved in 10 ml deionized water, pH be adjusted to 4 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 5:Cu
12(TMA)
8h
6pV
3mo
9o
40room Temperature Solid State synthetic
Get 0.24 gram of Cu (NO
3)
23H
2o and 0.5 gram of H
6pV
3mo
9o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 6:Cu
12(TMA)
8h
6pV
3mo
9o
40room Temperature Solid State synthetic
Get 0.2 gram of Cu (CH
3cOO)
2h
2o and 0.5 gram of H
6pV
3mo
9o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 7:Cu
12(TMA)
8h
6pV
3mo
9o
40room Temperature Solid State synthetic
Get 0.34 gram of CuCl
22H
2o and 0.5 gram of H
6pV
3mo
9o
40be dissolved in 10 ml deionized water, pH be adjusted to 4 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 8:Cu
12(TMA)
8h
6pV
3mo
9o
40room Temperature Solid State synthetic
Get 0.25 gram of CuSO
45H
2o and 0.5 gram of H
6pV
3mo
9o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 9:Cu
12(TMA)
8h
4pVMo
11o
40room Temperature Solid State synthetic
Get 0.24 gram of Cu (NO
3)
23H
2o and 0.5 gram of H
4pVMo
11o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 10:Cu
12(TMA)
8h
4pVMo
11o
40room Temperature Solid State synthetic
Get 0.2 gram of Cu (CH
3cOO)
2h
2o and 0.5 gram of H
4pVMo
11o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 11:Cu
12(TMA)
8h
4pVMo
11o
40room Temperature Solid State synthetic
Get 0.34 gram of CuCl
22H
2o and 0.5 gram of H
4pVMo
11o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 12:Cu
12(TMA)
8h
4pVMo
11o
40room Temperature Solid State synthetic
Get 0.25 gram of CuSO
45H
2o and 0.5 gram of H
4pVMo
11o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH, dry solution, obtain mix powder.The powder obtaining and 0.21 gram of mixed being incorporated in agate mortar of trimesic acid are ground, and it is green that mixed-powder gradually becomes.Wash green powder with water twice, ethanol washed twice, centrifugation, finally obtains loaded vanadium and replaces polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 13:Cu
12(TMA)
8h
5pV
2mo
10o
40room temperature liquid phase synthetic
Get 0.24 gram of Cu (NO
3)
23H
2o and 0.5 gram of H
5pV
2mo
10o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 14:Cu
12(TMA)
8h
5pV
2mo
10o
40room temperature liquid phase synthetic
Get 0.2 gram of Cu (CH
3cOO)
2h
2o and 0.5 gram of H
5pV
2mo
10o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 15:Cu
12(TMA)
8h
5pV
2mo
10o
40room temperature liquid phase synthetic
Get 0.34 gram of CuCl
22H
2o and 0.5 gram of H
5pV
2mo
10o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 16:Cu
12(TMA)
8h
5pV
2mo
10o
40room temperature liquid phase synthetic
Get 0.25 gram of CuSO
45H
2o and 0.5 gram of H
5pV
2mo
10o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 17:Cu
12(TMA)
8h
6pV
3mo
9o
40room temperature liquid phase synthetic
Get 0.24 gram of Cu (NO
3)
23H
2o and 0.5 gram of H
6pV
3mo
9o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 18:Cu
12(TMA)
8h
6pV
3mo
9o
40room temperature liquid phase synthetic
Get 0.2 gram of Cu (CH
3cOO)
2h
2o and 0.5 gram of H
6pV
3mo
9o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 19:Cu
12(TMA)
8h
6pV
3mo
9o
40room temperature liquid phase synthetic
Get 0.34 gram of CuCl
22H
2o and 0.5 gram of H
6pV
3mo
9o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 20:Cu
12(TMA)
8h
6pV
3mo
9o
40room temperature liquid phase synthetic
Get 0.25 gram of CuSO
45H
2o and 0.5 gram of H
6pV
3mo
9o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 21:Cu
12(TMA)
8h
4pVMo
11o
40room temperature liquid phase synthetic
Get 0.24 gram of Cu (NO
3)
23H
2o and 0.5 gram of H
4pVMo
11o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 22:Cu
12(TMA)
8h
4pVMo
11o
40room temperature liquid phase synthetic
Get 0.2 gram of Cu (CH
3cOO)
2h
2o and 0.5 gram of H
4pVMo
11o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 23:Cu
12(TMA)
8h
4pVMo
11o
40room temperature liquid phase synthetic
Get 0.34 gram of CuCl
22H
2o and 0.5 gram of H
4pVMo
11o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 24:Cu
12(TMA)
8h
4pVMo
11o
40room temperature liquid phase synthetic
Get 0.25 gram of CuSO
45H
2o and 0.5 gram of H
4pVMo
11o
40be dissolved in 10 ml deionized water, pH be adjusted to 3 with NaOH.Getting 0.21 gram of trimesic acid is dissolved in 10 milliliters of absolute ethyl alcohols.Under stirring, ethanolic solution is added drop-wise in the aqueous solution, in solution, engender green precipitate, will obtain green precipitate water and ethanol washed twice respectively, finally obtain loaded vanadium and replace polyacid porous nanocrystalline desulphurization catalyst.
Specific embodiment 25:Cu
12(TMA)
8h
5pV
2mo
10o
40catalytic oxidation desulfurization application
Get 0.147 gram of dibenzothiophenes and be dissolved in 50 milliliters of decahydronaphthalenes, heating and maintaining solution temperature is 80 degrees Celsius, adds 0.04 gram of Cu
12(TMA)
8h
5pV
2mo
10o
40nanocrystalline catalyst and 0.72 milliliter of isobutylaldehyde, in stirring, pass into oxygen by Bubbling method, react after 2 hours, monitor by chromatography of gases, dibenzothiophenes in decahydronaphthalene is all converted into dibenzothiophenes sulfone, centrifugation catalyst, adds 50 milliliters of acetonitrile extractions, can obtain deep desulfuration product.The conversion ratio of dibenzothiophenes relation is in time shown in accompanying drawing 6.
Claims (3)
1. loaded vanadium replaces the preparation method of polyacid desulphurization catalyst porous nanocrystalline, it is characterized in that room temperature liquid phase is synthetic, the Keggin type molybdophosphate that the soluble copper salt that is 3 ~ 4:1 by 1 gram of amount of substance ratio and vanadium replace is dissolved in 5 ~ 20 ml waters, pH is adjusted to 2 ~ 4, the trimesic acid that the ratio that takes the amount of substance of the Keggin type molybdophosphate replacing with vanadium is 1 ~ 2:1, be dissolved in 5 ~ 20 milliliters of ethanol, under agitation, the ethanolic solution of trimesic acid is added drop-wise in the aqueous solution of polyacid and mantoquita, in solution, engender green precipitate, centrifugation, washing, dry precipitation, finally obtain loaded vanadium and replace Keggin type molybdophosphate desulphurization catalyst porous nanocrystalline.
2. by preparation method claimed in claim 1, it is characterized in that described soluble copper salt is copper nitrate, Schweinfurt green, copper chloride, copper sulphate; The Keggin type molybdophosphate that vanadium replaces is: H
4pVMo
11o
40, H
5pV
2mo
10o
40and H
6pV
3mo
9o
40, the Keggin type molybdophosphate that vanadium replaces is respectively a replacement, two replacements and three replace vanadium.
3. loaded vanadium replaces the preparation method of polyacid desulphurization catalyst porous nanocrystalline, it is characterized in that Room Temperature Solid State is synthetic, the Keggin type molybdophosphate that the soluble copper salt that is 3 ~ 4:1 by 1 gram of amount of substance ratio and vanadium replace is dissolved in 5 ~ 20 ml waters, pH is adjusted to 2 ~ 4, solvent evaporated, obtain the mix powder of polyacid and mantoquita, the trimesic acid that the ratio that takes the amount of substance of the Keggin type molybdophosphate replacing with vanadium is 1 ~ 2:1, in agate mortar, mix and grind with above-mentioned powder, it is green that reactant color gradually becomes, water and ethanol is supersound washing post-drying product for several times respectively, finally obtain loaded vanadium and replace Keggin type molybdophosphate desulphurization catalyst porous nanocrystalline.
4. by preparation method claimed in claim 3, it is characterized in that described soluble copper salt is copper nitrate, Schweinfurt green, copper chloride, copper sulphate; The Keggin type molybdophosphate that vanadium replaces is: H
4pVMo
11o
40, H
5pV
2mo
10o
40and H
6pV
3mo
9o
40, the Keggin type molybdophosphate that vanadium replaces is respectively a replacement, two replacements and three replace vanadium.
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| CN107051583A (en) * | 2017-03-03 | 2017-08-18 | 赵建社 | Heteropoly acid, MOF and hollow molecules sieve tri compound desulphurization catalyst and preparation method thereof |
| CN107243361B (en) * | 2017-07-11 | 2020-05-08 | 东北师范大学 | Preparation method and application of polyacid-based metal organic framework nanocrystalline catalyst |
| CN110560171A (en) * | 2019-09-09 | 2019-12-13 | 沈阳师范大学 | Composite nanofiber with desulfurization performance and preparation method and application thereof |
| CN115124083B (en) * | 2022-07-27 | 2023-12-26 | 哈尔滨工业大学 | Keggin type heteropolyacid, preparation method thereof and application thereof in carbon reduction |
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