CN104001544A - Catalytic oxidation desulfurization catalyst and preparation method thereof - Google Patents
Catalytic oxidation desulfurization catalyst and preparation method thereof Download PDFInfo
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- CN104001544A CN104001544A CN201410264613.6A CN201410264613A CN104001544A CN 104001544 A CN104001544 A CN 104001544A CN 201410264613 A CN201410264613 A CN 201410264613A CN 104001544 A CN104001544 A CN 104001544A
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Abstract
The invention discloses a catalytic oxidation desulfurization catalyst and a preparation method thereof. The chemical formula of the catalytic oxidation desulfurization catalyst is (Cn-Cs-Cn)2 Y XM12O40), wherein Cn-Cs-Cn is a gemini surfactant, the spacer s is equal to 2 or 4 or 6, the alkyl chain n is equal to 14 o 16 or 18, the counter anion atom Y is a halogen atom, the heteroatom X is phosphorus or silicon or boron or iron or cobalt or arsenic or germanium, and the donor atom M is molybdenum or tungsten. The catalytic oxidation desulfurization catalyst not only is suitable for oxidation desulfurization of sulfur-containing organic matter, but also extends emulsion to the other organic synthesis fields, such as reactions of alkene epoxidation, alcohol oxidation, acid catalysis and isomerization. As long as the system is conducted in the oil-water two-phase, and the suitable heteropolyacid and the gemini surfactant with the suitable alkyl chain length and the suitable spacer length are adopted, the catalyst high in catalytic efficiency can be formed; after the reaction, the catalyst can be separated out through static demulsification; after the catalyst is recycled ten times, the catalytic efficiency can still be kept to be 95.7% of original catalytic efficiency.
Description
Technical field
The present invention relates to a kind of emulsion catalyst system and catalyzing for organic sulfur compound oxidation can be recycled and preparation method thereof, be specifically related to a kind of capable of circulation, reusable catalytic oxidation desulfurization Catalysts and its preparation method that double type surfactant and polyacid compound be prepared from as raw material of take.
Background technology
Gasoline and Ultra-deep Desulfurization of Diesel Fuels have become one of research topic of being badly in need of in world wide solution.Sulfide in fuel oil, inevitably in the process of burning, the form with gas has been discharged in air.These oxide gas and airborne moisture react and raw can form sulfate, and then form acid rain, damage building, and acidified soil, causes the degeneration of forest, destroys the ecosystem.Thereby exploitation Ultra-deep Desulfurization of Diesel Fuels research tool is of great significance.Gasoline and Ultra-deep Desulfurization of Diesel Fuels are not only in order to produce clean fuel, and use aspect sulphur hydrogen and also have potential application at production fuel cell.
Be considered to the very desulfur technology of attraction and have extract and separate or absorption, desulfurization via selective oxidation and biological desulphurization etc.Oxidation sweetening is comprised of two key steps conventionally: the first step is by the sulfide oxidation in fuel oil, and second step is removed the sulfide of oxidation from fuel oil by method separation such as extraction, absorption, distillations.Because oxidation sweetening does not need hydrogen source, the investment of comparing with other hydrodesulfurizations is less, and the investment of the reaction temperature that oxidation sweetening needs in addition, pressure force-summing device is well below hydrodesulfurization.
Sulphur has much similar character with oxygen, and the hydrocarbon of the character that organic sulfur compound shows and their correspondences is closely similar, almost identical with the solubility in solvent at water.Organic oxygen compound but shows the dissolubility stronger than organic sulfur compound in organic solvent, if oxygen molecule is connected on the sulphur atom of these sulfide, their polarity will strengthen greatly, thereby causes the solubility in polar solvent to increase.A large amount of researchs show, the sulfide in diesel oil and oxidant are had an effect, and sulfide is converted into after corresponding sulfone and sulfoxide, can greatly carry high molecular dipole moment, and polarity increases, thereby can greatly improve extraction (or absorption) desulfuration efficiency.Hydrogen peroxide is a kind of very promising oxidant, and hydrogen peroxide is mixed problem as the obstacle of catalyst maximum, and hydrogen peroxide is present in water, and sulfide is but present in organic phase.
Emulsion is the important dispersion of a class, in fields such as the energy, chemical industry, food, medicine, agricultural chemicals, cosmetics, is widely used.In liquid-liquid two-phase system, the reaction rate of oxidizing process had both been decided by the intrinsic reaction rate of reaction, was subject to again the impact of mass transfer rate.For they are better mixed, researchers have adopted many kinds of measures, as add surfactant, acceleration stirring, ultrasonic emulsification etc.In general, hydrogen peroxide is liquid-liquid two phase reaction during as the oxidation desulfur reaction of oxidant, but that the shortcoming of two-phase system is reaction rate is slow.Widely accepted method is to add a surfactant, and it can be dissolved in reagent or form milky dispersion system.In emulsion system, the micelle being formed by surfactant molecule provides the larger specific area of reaction needed, and the steric effect being caused by mass transfer greatly reduces, so emulsion or microemulsion system can improve reaction rate effectively.In addition, in principle, by changing reaction temperature, water oil two, compare, the HLB value of surfactant, can make surfactant-dispersed on the surface of emulsion droplet, in reaction, keep stable, reaction finishes rear emulsion droplet can breakdown of emulsion, and surfactant is gathered on the interface of water oil two-phase, thereby is easy to separation, recycling.
Conventionally the surfactant adopting has Cetyltrimethylammonium bromide (STAB) and DDA (DODA), these surfactants with single center of positive charge, there are one or two alkyl chains.In the catalyst structure of this class synthesis of surfactant, alkyl chain the density of catalytic active center be not too low be exactly too high, cannot take into account the formation at active peroxide center and the contact catalysis center of low polarity sulfide simultaneously.According to forefathers' document and patent report, when the density of alkyl chain parcel polyacid is lower, although be conducive to the catalytic center that hydrogen peroxide contacts many acid forming activities, be unfavorable for contacting of low polarity sulfurous organic compound and catalyst, reduced the catalytic capability of catalyst; When the density of alkyl chain parcel polyacid is higher, can seriously hinder oxidant heteropolyacid salt is oxidized to peroxide multi-acid salt, be also unfavorable for improving the catalytic activity of catalyst.Therefore, prepare the rational polyacid hybrid material of a kind of alkyl chain bulk density and the degree of order, its structure is the formation at balance peroxide center and the diffusion of low polarity sulfide dexterously, is a large study hotspot that improves polyacid base catalytic oxidation desulfurization catalyst.
Summary of the invention
The object of this invention is to provide a kind of catalytic oxidation desulfurization Catalysts and its preparation method, this catalyst system and catalyzing can be got rid of the sulphur content in sulfurous organic compound efficiently in emulsion, and catalyst is easy and product separation and recovery.
The object of the invention is to be achieved through the following technical solutions:
A catalytic oxidation desulfurization catalyst, adopts double type surfactant parcel to have the H of Keggin structure
3xM
12o
40polyacid, thus (XM formed
12c
18c
n: n=2,4,6) heteropolyacid salt compound, be finally prepared into expression formula for (C
n-C
s-C
n)
2y (XM
12o
40) catalyst, C wherein
n-C
s-C
nfor in the present invention according to the synthetic double type surfactant of document, interval base s=2,4 or 6, alkyl chain n=14,16 or 18.Heteropolyanion is the compound or derivatives thereof with the Keggin structure of Keggin structure or omission, and counter anion atom Y is halogen atom, and as Br, Cl etc., hetero atom X is phosphorus, silicon, boron, iron, cobalt, arsenic, germanium etc., and joining atom M is molybdenum or tungsten.
Above-mentioned catalyst is mainly used in emulsion catalyst system and catalyzing, and this system be take water as solvent, and 30% hydrogen peroxide is oxidant, and the compound of heteropolyacid salt is that catalyst carries out desulfurization catalysis.
Above-mentioned catalyst system and catalyzing is for the synthetic method of catalytic oxidation desulfurization catalyst, and its key step is:
1) according to the synthetic C of document
n-C
s-C
ntype double type surfactant (alkyl chain n=14,16,18; Interval base s=2,4,6): by the N of 4.5-7mmol, N, N, N-tetramethylethylenediamine is added drop-wise to 4-8mmol, contains 2, in the ethanolic solution of the halogenated hydrocarbons of 4,6 alkyl chains, then at 40-100 ℃, stir 48-72h, then with Rotary Evaporators, dry, finally in the miscible agent of chloroform/ethyl acetate, crystallization obtains C
n-C
s-C
ntype double type surfactant;
2) by 1.5-3mmola) prepared C
n-C
s-C
ntype double type surfactant dissolves with the ethanol of 40-70mL.Then slowly drip the H of 0.5-2mmol, 5-30mg/mL
3xM
12o
40in ethanolic solution, stir 6-24h, then suction filtration, uses ethanol and deionized water cyclic washing 3 times, finally obtains the composite catalyst XM of novel gemini surfactants and polyacid
12c
18c
n(n=2,4,6), drying for standby;
3) solvent, mould oil and oxidant are put into the round-bottomed flask reactor with reflux, then added reactant and polyacid composite catalyst XM
12c
18c
n, then under 40-80 ℃, 400-1000rpm rotating speed, stir, form emulsion; Wherein the ratio of oxidant/reactant/catalyst is 20-25/1-3/0.01-0.015.The consumption judgement reaction end that utilizes thin-layered chromatography and gas chromatography monitoring sulfide, the reaction time, between 20-115 minute, stops stirring.
4) after reaction finishes, by standing, water oil content layer, then extract catalyst by the method for suction filtration.The thick catalyst extracting is cleaned 3-5 time with ethanol, then in vacuum drying chamber, be dried, finally obtain the composite catalyst XM of recoverable novel gemini surfactants and polyacid
12c
18c
n(n=2,4,6).
In said method, described reactant is mainly organosulfur compound, comprises and is not limited to thiophene, benzothiophene, dibenzothiophenes and 4,6-dimethyl Dibenzothiophene, dimethyl sulfide, diethyl sulfide etc.
In said method, described double type surfactant is C
18-C
2-C
18, C
18-C
4-C
18, C
18-C
6-C
18, its preparation method is as follows:
C
18-C
2-C
18preparation: by bromo-octadecane (1.834g, 5.5mmol, 1equiv) be added in the round-bottomed flask of 100ml, splash into N, N, N, N-tetramethylethylenediamine (0.745ml, 5mmol, 0.9equiv), use the ethanol of 50ml as solvent, and add hot reflux in the oil bath of 80 ℃, reaction 48-72h.After reaction finishes, by organic solvent evaporated under reduced pressure, then use the mixed solvent recrystallization of chloroform/ethyl acetate more than 3 times, obtain white solid 1.33g, productive rate is 55%.
C
18-C
4-C
18preparation: by N, Dymanthine (1.64g, 5.5mmol, 1equiv) and Isosorbide-5-Nitrae-dibromobutane (1.08g, 5mmol, 0.9equiv) join in the round-bottomed flask of 100ml, and add the ethanolic solution of 50ml as solvent, in the oil bath of 80 ℃, add hot reflux, reaction 48-72h.After question response finishes, by organic solvent evaporated under reduced pressure, use ethyl acetate cyclic washing 2 times, then use the mixed solvent recrystallization of chloroform/ethyl acetate more than 3 times, obtain white solid 1.66g, productive rate is 61%.
C
18-C
6-C
18preparation: by N, Dymanthine (1.64g, 5.5mmol, 1equiv) with 1,6-dibromo-hexane (1.27g, 5mmol, 0.9equiv) join in the round-bottomed flask of 100ml, and add the ethanolic solution of 50ml as solvent, in the oil bath of 80 ℃, add hot reflux, reaction 48-72h.After question response finishes, by organic solvent evaporated under reduced pressure, use ethyl acetate cyclic washing 2 times, then use the mixed solvent recrystallization of chloroform/ethyl acetate more than 3 times, obtain white solid 1.97g, productive rate is 60%.
In said method, described catalyst can be (C
18-C
2-C
18)
2br (AsMo
12o40), (C
18-C
4-C
18)
2br (AsMo
12o40), (C
18-C
6-C
18)
2br (AsMo
12o40), (C
18-C
2-C
18)
2br (AsW
12o40), (C
18-C
2-C
18)
2br (PMo
12o40), (C
18-C
2-C
18)
2br (PW
12o40).
In said method, described hetero atom X can be phosphorus, silicon, boron, iron, cobalt, arsenic, germanium etc., and joining atom M can be molybdenum or tungsten.
In said method, described oxidant is hydrogen peroxide.
In said method, described solvent is deionized water.
In said method, described mould oil is mainly nonpolar alkane, and other and solvent and the immiscible organic matter of reactant; Described nonpolar alkane is hexadecane, the tetradecane, dodecane, normal octane, n-hexane etc.
Catalyst system and catalyzing of the present invention, when catalytic oxidation organic molecule, comprises immiscible two-phase liquid, amphiphatic catalyst and reactant.Amphiphilic catalyst is in two-phase interface self assembly, and hydrophobic alkyl chain points to oil phase, and catalytic center points to water, and oxidation reaction occurs in the interface of two-phase.After question response completes, reaction emulsion can be by standing, two phase stratification, and catalyst is insoluble in two-phase or product, catalyst easily with product separation recovery, can realize repeatedly and repeat, recycle.
Amphiphatic catalyst be by the surfactant with center of positive charge and with the heteropolyacid salt of center of negative charge by electrostatic attraction effect combination.General heteropolyacid salt has stronger hydrophily, and catalyst hydrophilic-hydrophobic balance can, according to the feature of reaction system, be regulated by the quantity of the organic molecule of modifying or type and the carbon chain lengths of surfactant functional group, thereby reach amphiphatic design.Selected surfactant root, according to the difference of actual demand, can be ionic surfactant, non-ionic surface active agent or high molecular surfactant.
Be that with the difference of the document of having reported and patent surfactant involved in the present invention is to have two center of positive charge, interval base that one can regulate and control and the double type surfactant of two alkyl chains, its expression formula is C
n-C
s-C
n.Double charge center can regulate and control alkyl chain in polyacid catalytic center bulk density around, the length of alkyl chain n can regulate the hydrophobic performance of double type surfactant, the length of regulation and control midfeather base can realize the regulation and control that alkyl chain is piled up the degree of order, thereby realizes the object that regulates and controls more efficiently catalyst performance.Compare the surfactant with single center of positive charge, double type surfactant can be arranged more regularly on the surface of heteropolyacid salt, thereby suitable alkyl chain bulk density also effectively balance entering of hydrogen peroxide form active peroxyl species, and improve contacting and reacting of sulfurous organic compound and the peroxide multi-acid salt forming in course of reaction, thereby catalytic efficiency and the catalytic selectivity of catalyst integral body have been improved.In addition, due to related in the present invention be emulsion catalyst system and catalyzing, reaction occurs in boundary, due to the high-specific surface area of decentralized photo, emulsion catalyst system and catalyzing is very similar to homogeneous catalytic reaction.
In catalytic oxidation desulfurization reaction system involved in the present invention, used is that solvent is water, rather than poisonous halogenated hydrocarbons or aromatic hydrocarbons, process environmental protection.After having reacted, only need can complete breakdown of emulsion by static, reactant liquor layering, catalyst is insoluble to arbitrary phase wherein, can complete the recycling that repeats of catalysis by simple suction filtration, washing, and experimental result also shows, catalyst prepared by the present invention has good cyclical stability, reuse after ten times, its catalytic efficiency still can remain to 95.7% of former catalytic efficiency, and in 20-30min, this catalyst can be removed the dibenzothiophenes in system completely.In the emulsion system forming at above-mentioned catalyst, the special molecular structure of double type surfactant dexterously balance the formation of peroxide multi-acid salt, and benzothiophene, dibenzothiophenes, 4, the absorption of the low polarity sulfurous organic compounds such as 6-dimethyl Dibenzothiophene, thus the catalytic activity of this catalyst improved.
The present invention is not only applicable to the oxidation sweetening of sulfurous organic compound, emulsion can also be expanded to the fields such as other organic syntheses, in the multiple reactions such as the oxidation of alkene epoxidation, alcohol, acid catalysis, isomerization.As long as relate to system carries out in profit two-phase, by applicable heteropoly acid and applicable alkyl chain length, be applicable to the double type surfactant of Length of spacer, all likely form the catalyst with high catalytic efficiency, after reaction, by static breakdown of emulsion, can by catalyst separation out, be cycled to repeat utilization.
The present invention has following advantage:
1. the present invention relates to a kind of surfactant with two center of positive charge, not only can regulate and control by changing the constituent of heteropoly acid the oxidation susceptibility of catalyst, can also be by the length of alkyl chain in regulation and control double type surfactant, the length of interval base more effectively realizes design and the assembling of catalyst on molecular level;
2. compare the surfactant with single center of positive charge, double type surfactant is except regulating and controlling better the hydrophobic performance of catalyst, can also arrange more regularly on the surface of heteropolyacid salt, the alkyl chain density on regulation and control catalytic center surface, thereby improved contacting and reacting of sulfurous organic compound and the peroxide multi-acid salt forming in course of reaction, thereby improved catalytic efficiency and the catalytic selectivity of catalyst integral body;
3. the emulsion system relating in the present invention, reaction occurs in two-phase interface, has higher specific area, makes reaction rate and homogeneous catalytic reaction similar;
4., after catalytic reaction finishes, can only by the static method of physics, realize breakdown of emulsion, thus realize catalyst and reactant separated, recycle;
5. the present invention is not only applicable to the oxidation sweetening of sulfurous organic compound, can also be according to the actual demand of catalytic reaction type, select the double type surfactant of applicable heteropoly acid and applicable alkyl chain length, applicable Length of spacer, all likely form the catalyst with high catalytic efficiency.
Accompanying drawing explanation
Fig. 1 is AsMo
12c
18c
2under different hydrogen oxide input amounts, remove the reaction time that DBT needs completely;
Fig. 2 is AsMo
12c
18c
2when differential responses, temperature is removed the reaction time of DBT completely;
Fig. 3 is different (C
18-C
2-C
18)
2br (AsMo
12o40) remove completely the reaction time of DBT;
Fig. 4 is the change curve of DBT inversion quantity with the reaction time;
Fig. 5 is ln (C
t/ C
0) with the change curve in reaction time;
Fig. 6 is (C
18-C
2-C
18)
2br (AsMo
12o
40) conversion ratio and the ln (C of BT of catalysis same amount
t/ C
0) curve over time;
Fig. 7 is (C
18-C
2-C
18)
2br (AsMo
12o
40) catalysis same amount, 4, the conversion ratio of 6-DMBT and ln (C
t/ C
0) curve over time;
Fig. 8 is that the complete catalysis DBT of different catalysts transforms the corresponding time;
Fig. 9 is the inversion quantity of catalyst catalysis DBT in difference recycles number of times 25min.
The specific embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but do not limit to so; every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1
Catalyst (C
18-C
2-C
18)
2br (AsMo
12o
40) preparation:
As an illustrative examples, catalyst (C
18-C
2-C
18)
2br (AsMo
12o
40) can prepare as follows: 5.5mmol1-bromo-octadecane is dissolved in the ethanolic solution of 50mL, then slowly drip the N of 5mmol, N, N, N-tetramethylethylenediamine, then in the oil bath of 80 ℃, stir, heat 48h, finally use Rotary Evaporators evaporate to dryness, and crystallization obtains C in chloroform/ethyl acetate system
18-C
2-C
18; By the C of the 0.096mmol obtaining
18-C
2-C
18be dissolved in the ethanolic solution of 5mL, then slowly add the H of 0.048mmol
3asMo
12o
40, obtain the sediment (C of bright yellow
18-C
2-C
18)
2br (AsMo
12o
40) (referred to as AsMo
12c
18c
2), then react 12h, finally by suction filtration, washing, dry method, obtain AsMo
12c
18c
2, yield is about 62%.C in course of reaction
18-C
2-C
18with H
3asMo
12o
40mol ratio be 2:1, according to charge balance and molecular structure matching principle, the polyoxoanion of negative 3 valencys needs the cation Gemini molecular equilibrium of 2 positive divalents, not enough negative electrical charge relies on a halide anion to supply.
Embodiment 2
As an illustrative examples, catalyst (C
18-C
4-C
18)
2br (AsMo
12o
40) preparation:
With embodiment 1, with N, N-dimethyl octadecylamine acetate, Isosorbide-5-Nitrae-dibromoalkane, H
3asMo
12o
40synthetic (C
18-C
4-C
18)
2br (AsMo
12o
40).
By 5.5mmol1,4-dibromoalkane is dissolved in the ethanolic solution of 50mL, then slowly drips the N of 5mmol, N, N, N-tetramethylethylenediamine, then in the oil bath of 80 ℃, stir, heat 48h, finally use Rotary Evaporators evaporate to dryness, and crystallization obtains C in chloroform/ethyl acetate system
18-C
4-C
18; By the C of the 0.096mmol obtaining
18-C
4-C
18be dissolved in the ethanolic solution of 5mL, then slowly add the H of 0.048mmol
3asMo
12o
40, obtain the sediment of bright yellow, then react 12h, finally by suction filtration, washing, dry method, obtain (C
18-C
4-C
18)
2br (AsMo
12o
40).
Embodiment 3
As an illustrative examples, catalyst (C
18-C
6-C
18)
2br (AsMo
12o
40) preparation:
With embodiment 1, with N, N-dimethyl octadecylamine acetate, Isosorbide-5-Nitrae-dibromo-hexane, H
3asMo
12o
40synthetic (C
18-C
6-C
18)
2br (AsMo
12o
40).
By 5.5mmol1,4-dibromo-hexane is dissolved in the ethanolic solution of 50mL, then slowly drips the N of 5mmol, N, N, N-tetramethylethylenediamine, then in the oil bath of 80 ℃, stir, heat 48h, finally use Rotary Evaporators evaporate to dryness, and crystallization obtains C in chloroform/ethyl acetate system
18-C
6-C
18; By the C of the 0.096mmol obtaining
18-C
6-C
18be dissolved in the ethanolic solution of 5mL, then slowly add the H of 0.048mmol
3asMo
12o
40, obtain the sediment of bright yellow, then react 12h, finally by suction filtration, washing, dry method, obtain (C
18-C
6-C
18)
2br (AsMo
12o
40).
Embodiment 4
As an illustrative examples, catalyst for control experiment (STAB)
3asMo
12o
40(DODA)
3asMo
12o
40preparation:
Respectively (0.144mmol) Cetyltrimethylammonium bromide (STAB) or DDA (DODA) are dissolved in the ethanolic solution of 5mL, then slowly add the H of 10mL (90mg, 0.048mmol)
3asMo
12o
40, obtain the sediment of bright yellow, then react 12h, finally by suction filtration, deionized water washing, dry method, obtain (STAB)
3asMo
12o
40, (DODA)
3asMo
12o
40.
Embodiment 5
The object of the present embodiment is the analytical method for research model oil sulfur content:
We are by benzothiophene (BT), dibenzothiophenes (DBT), 4,6-dimethyl dibenzo thiophene (4,6-DMDBT) these three kinds of compounds, take n-hexane as solvent, the mould oil of configuration variable concentrations, use Tianmei GC7900 gas chromatograph system (GC), to each compound drawing standard curve.Vapor detection all adopts the method for temperature programming, and pillar is SE-54 capillary gas chromatographic column.The detected parameters of benzothiophene (BT) is: 250 ℃ of injector temperatures, 150 ℃ of post case temperature, 250 ℃ of detector temperatures.Heating schedule is: 5 ℃/min rises to 190 ℃ and retains 2min, and 5 ℃/min rises to 250 ℃ and retains 25min, and appearance time is 4.3min.The detected parameters of dibenzothiophenes (DBT) is: 250 ℃ of injector temperatures, 210 ℃ of post case temperature, 250 ℃ of detector temperatures.Heating schedule is: 5 ℃/min rises to 230 ℃ and retains 5min, and 5 ℃/min rises to 250 ℃ and retains 25min, and appearance time is 6.46min.(4, detected parameters 6-DMDBT) is 4,6-dimethyl Dibenzothiophene: 250 ℃ of injector temperatures, 220 ℃ of post case temperature, 250 ℃ of detector temperatures.Heating schedule is: 5 ℃/min rises to 230 ℃ and retains 3min, and 5 ℃/min rises to 250 ℃ and retains 25min, and appearance time is 8.6min.
Embodiment 6
The object of the present embodiment is in order to study the impact of different oxidant concentrations on catalytic efficiency.
Get five group of 3.13 μ mol (C
18-C
2-C
18)
2br (AsMo
12o
40) and 1527ppm DBT join in the round-bottomed flask of 50mL, then add respectively the H of 0.1,0.2,0.4,0.6,0.8mL30%
2o
2solution, reactant liquor all reacts under the condition of the oil bath at 60 ℃, 800rpm/min, in course of reaction, samples at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, and the test result of different oxidant concentrations is listed in Fig. 1.
As can be seen from Figure 1, when the content of hydrogen peroxide is 0.6mL, the corresponding reaction time is the shortest is 25min.
Embodiment 7
The object of the present embodiment is in order to study the impact of differential responses temperature on catalytic efficiency.
Get 3.13 μ mol (C
18-C
2-C
18)
2br (AsMo
12o
40) and 1527ppm DBT join in the round-bottomed flask of 50mL, then add respectively the H of 0.6mL30%
2o
2solution, reactant liquor, 40,50, reacts under the oil bath of 60,70,80 ℃, the condition of 800rpm/min.In course of reaction, sample at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, the test result of differential responses temperature is listed in Fig. 2.
As can be seen from Figure 2, within the scope of 40-70 ℃, along with rising reaction time of reaction temperature reduces, but when reaction temperature continues to be increased to 80 ℃, the reaction time increases again to some extent.When reaction temperature is 70 ℃, the reaction time is 20min.
Embodiment 8
The object of the present embodiment is in order to study the impact of different catalysts content on catalytic efficiency.
Get respectively 6,8,10,15, (the C of 20mg
18-C
2-C
18)
2br (AsMo
12o
40) be added to respectively in the round-bottomed flask of five two mouthfuls, then to the DBT that adds reactant 271 μ mol in each bottle, 50mL n-hexane, the H of 0.6mL30%
2o
2solution, reactant liquor reacts under the condition of the oil bath of 60 ℃, 800rpm/min, in course of reaction, samples at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, five kinds of test results with the catalyst of different interval base are listed in Fig. 3.
As can be seen from Figure 3, along with (C
18-C
2-C
18)
2br (AsMo
12o
40) increase, the catalytic reaction time is shorter.
Embodiment 9
The object of the present embodiment is in order to study the impact of different interval base length on catalytic efficiency in double type surfactant.
Get (C
18-C
2-C
18)
2br (AsMo
12o
40), (C
18-C
4-C
18)
2br (AsMo
12o
40), (C
18-C
6-C
18)
2br (AsMo
12o
40) each 3.13 μ mol are added to respectively in the round-bottomed flask of three two mouthfuls, then to the DBT that adds reactant 271 μ mol in each bottle, 50mL n-hexane, the H of 0.6mL30%
2o
2solution, reactant liquor reacts under the condition of the oil bath of 60 ℃, 800rpm/min, in course of reaction, samples at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, five kinds of test results with the catalyst of different interval base are listed in Fig. 4-5.
From Fig. 4-5, can find out, along with the increase of interval base, the reaction time increases gradually, and when interval base is 2 methylene, catalytic efficiency is the highest.
Embodiment 10
The object of the present embodiment is for the contrast of comparative study catalyst of the present invention to differential responses substrate catalytic efficiency.
Get 3.13 μ mol (C
18-C
2-C
18)
2br (AsMo
12o
40), 1572ppm BT and 1572ppm4,6-DMBT joins respectively in the round-bottomed flask of 50mL, then adds respectively the H of 0.6mL30%
2o
2solution, reactant liquor reacts under the condition of the oil bath of 60 ℃, 800rpm/min, in course of reaction, samples at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, and the test result of differential responses thing is listed in Fig. 6-7.
Embodiment 11
The object of the present embodiment is in order to study the contrast of the custom catalysts catalytic efficiency in catalyst of the present invention and document and patent.
Get 3.13 μ mol (C
18-C
2-C
18)
2br (AsMo
12o
40), (C
18-C
4-C
18)
2br (AsMo
12o
40), (C
18-C
6-C
18)
2br (AsMo
12o
40), (STAB)
3asMo
12o
40, (DODA)
3asMo
12o
40join respectively in five round-bottomed flasks, then to the DBT that adds reactant 271 μ mol in each bottle, 50mL n-hexane, the H of 0.6mL30%
2o
2solution, reactant liquor reacts under the condition of the oil bath of 60 ℃, 800rpm/min.In course of reaction, sample at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, the test result of three kinds of catalyst is listed in Fig. 8.
As can be seen from Figure 8, under the same conditions, (C
18-C
2-C
18)
2br (AsMo
12o
40), (C
18-C
4-C
18)
2br (AsMo
12o
40) (C
18-C
6-C
18)
2br (AsMo
12o
40), catalytic efficiency apparently higher than conventional catalyst (STAB)
3asMo
12o
40(DODA)
3asMo
12o
40.
Embodiment 12
The object of the present embodiment is the recycling for Study of Catalyst.
Get oil phase after creaming of emulsion and middle solid catalyst layer, without any processing, directly join in the round-bottomed flask of two mouthfuls, add respectively the DBT of 271 μ mol, 50mL n-hexane, the H of 0.6mL30%
2o
2solution, reactant liquor reacts under the condition of the oil bath of 60 ℃, 800rpm/min, in course of reaction, samples at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, and catalyst circulation is used and be the results are shown in Fig. 9.
As can be seen from Figure 9, catalyst is after ten circulations, and the inversion quantity of its catalysis DBT still can remain to 95.7%, illustrates that the prepared catalyst of the present invention has good recycling.
Embodiment 13
Catalyst (C
18-C
2-C
18)
2br (PW
12o
40) preparation:
As an illustrative examples, catalyst (C
18-C
2-C
18)
2br (PW
12o
40) can prepare as follows: C
18-C
2-C
18synthetic according to route under embodiment 1; By the C of the 0.096mmol obtaining
18-C
2-C
18be dissolved in the ethanolic solution of 5mL, then slowly add the H of 0.048mmol
3pW
12o
40, obtain linen sediment, then react 12h, finally by suction filtration, washing, dry method, obtain (C
18-C
2-C
18)
2br (PW
12o
40), yield is about 70%.
Embodiment 14
The object of the present embodiment is in order to study the not impact of isopolyacid on catalytic efficiency.
Get respectively (the C of 3.13 μ mol
18-C
2-C
18)
2br (PW
12o
40) be added in the round-bottomed flask of two mouthfuls, then to the DBT that adds reactant 271 μ mol in each bottle, 50mL n-hexane, the H of 0.6mL30%
2o
2solution, reactant liquor reacts under the condition of the oil bath of 60 ℃, 800rpm/min, in course of reaction, samples at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, and DBT is converted into DBTO completely
2the time of (dibenzothiophenes sulfone) is 19min.
Embodiment 15
Catalyst (C
18-C
2-C
18)
2br (PMo
12o
40) preparation:
As an illustrative examples, catalyst (C
18-C
2-C
18)
2br (PMo
12o
40) can prepare as follows: C
18-C
2-C
18synthetic according to route under embodiment 1; By the C of the 0.096mmol obtaining
18-C
2-C
18be dissolved in the ethanolic solution of 5mL, then slowly add the H of 0.048mmol
3pMo
12o
40, obtain yellow sediment, then react 12h, finally by suction filtration, washing, dry method, obtain (C
18-C
2-C
18)
2br (PMo
12o
40), yield is about 59%.
Embodiment 16
The object of the present embodiment is in order to study the not impact of isopolyacid on catalytic efficiency.
Get respectively (the C of 3.13 μ mol
18-C
2-C
18)
2br (PMo
12o
40) be added in the round-bottomed flask of two mouthfuls, then to the DBT that adds reactant 271 μ mol in each bottle, 50mL n-hexane, the H of 0.6mL30%
2o
2solution, reactant liquor reacts under the condition of the oil bath of 60 ℃, 800rpm/min, in course of reaction, samples at set intervals, then it is carried out to concentration analysis, gas chromatographic analysis, and DBT is converted into DBTO completely
2the time of (dibenzothiophenes sulfone) is 29min.
Claims (10)
1. a catalytic oxidation desulfurization catalyst, the expression formula that it is characterized in that described catalyst is (C
n-C
s-C
n)
2y (XM
12o
40), C wherein
n-C
s-C
nfor double type surfactant, interval base s=2,4 or 6, alkyl chain n=14,16 or 18; Counter anion atom Y is halogen atom; Hetero atom X is phosphorus, silicon, boron, iron, cobalt, arsenic or germanium; Joining atom M is molybdenum or tungsten.
2. catalytic oxidation desulfurization catalyst according to claim 1, the expression formula that it is characterized in that described catalyst is (C
18-C
2-C
18)
2br (AsMo
12o40), (C
18-C
4-C
18)
2br (AsMo
12o40), (C
18-C
6-C
18)
2br (AsMo
12o40), (C
18-C
2-C
18)
2br (AsW
12o40), (C
18-C
2-C
18)
2br (PMo
12o40) or (C
18-C
2-C
18)
2br (PW
12o40).
3. catalytic oxidation desulfurization catalyst according to claim 1, is characterized in that described C
n-C
s-C
nfor C
18-C
2-C
18, C
18-C
4-C
18or C
18-C
6-C
18.
4. catalytic oxidation desulfurization catalyst according to claim 1, is characterized in that described halogen is Br or Cl.
5. a preparation method for the catalytic oxidation desulfurization catalyst described in the arbitrary claim of claim 1-4, is characterized in that described method step is as follows:
1) synthetic C
n-C
s-C
ntype double type surfactant;
2) by 1.5-3mmol step 1) prepared C
n-C
s-C
ntype double type surfactant dissolves with the ethanol of 40-70mL, then slowly drips the H of 0.5-2mmol, 5-30mg/mL
3xM
12o
40in ethanolic solution, stir 6-24h, then suction filtration, with ethanol and deionized water cyclic washing, finally obtains composite catalyst XM
12c
18c
n, drying for standby;
3) solvent, mould oil and oxidant are put into the round-bottomed flask reactor with reflux, then added reactant and composite catalyst XM
12c
18c
n, then under 40-80 ℃, 400-1000rpm rotating speed, stir, form emulsion, wherein the ratio of oxidant/reactant/catalyst is 20-25/1-3/0.01-0.015; The consumption judgement reaction end that utilizes thin-layered chromatography and gas chromatography monitoring sulfide, the reaction time, between 20-115 minute, stops stirring;
4) after reaction finishes, by standing, water oil content layer, then extract catalyst by the method for suction filtration, and the thick catalyst extracting is cleaned 3-5 time with ethanol, then in vacuum drying chamber, be dried, finally obtain the composite catalyst XM of recoverable
12c
18c
n.
6. the preparation method of catalytic oxidation desulfurization catalyst according to claim 5, is characterized in that described reactant is organosulfur compound.
7. the preparation method of catalytic oxidation desulfurization catalyst according to claim 6, is characterized in that described organosulfur compound is thiophene, benzothiophene, dibenzothiophenes and 4,6-dimethyl Dibenzothiophene, dimethyl sulfide or diethyl sulfide.
8. the preparation method of catalytic oxidation desulfurization catalyst according to claim 5, is characterized in that described solvent is deionized water.
9. the preparation method of catalytic oxidation desulfurization catalyst according to claim 5, is characterized in that described mould oil is the immiscible organic matter of nonpolar alkane or other and solvent and reactant.
10. the preparation method of catalytic oxidation desulfurization catalyst according to claim 9, is characterized in that described nonpolar alkane is hexadecane, the tetradecane, dodecane, normal octane or n-hexane.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986778A (en) * | 2017-03-03 | 2017-07-28 | 赵建社 | Surfactant type heteropoly acid and its preparation method and application |
| 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 |
| WO2018205113A1 (en) * | 2017-05-08 | 2018-11-15 | Solvay Sa | Process for removing sulfur compounds from a liquid composition |
| US11225613B2 (en) * | 2017-05-08 | 2022-01-18 | Solvay Sa | Process for removing sulfur compounds from a liquid composition |
| CN107968153A (en) * | 2017-11-20 | 2018-04-27 | 武汉华星光电半导体显示技术有限公司 | A kind of OLED device and preparation method |
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| CN112337492A (en) * | 2020-11-19 | 2021-02-09 | 营口理工学院 | Preparation method of polyoxometallate heterogeneous oxidation desulfurization catalyst |
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