CN106378187A - Ionic liquid covalently modified polyacid intercalated hydrotalcite and application thereof in deep desulfurization of oil products - Google Patents
Ionic liquid covalently modified polyacid intercalated hydrotalcite and application thereof in deep desulfurization of oil products Download PDFInfo
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- CN106378187A CN106378187A CN201610730606.XA CN201610730606A CN106378187A CN 106378187 A CN106378187 A CN 106378187A CN 201610730606 A CN201610730606 A CN 201610730606A CN 106378187 A CN106378187 A CN 106378187A
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- hydrotalcite
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
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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
- C10G2300/70—Catalyst aspects
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Abstract
The invention discloses an ionic liquid covalently modified polyacid intercalated hydrotalcite and application thereof in deep desulfurization of oil products. The preparation method of the ionic liquid covalently modified polyacid intercalated hydrotalcite includes: firstly preparing a hydrotalcite precursor and stripping the precursor with a formamide solution to form a colloidal solution; then conducting covalent modification to bond the ionic liquid to the peeled hydrotalcite nanosheet layer; then utilizing the electrostatic interaction of rare earth polyacid and the hydrotalcite nanosheet layer to conduct ordered assembly, thus forming rare earth polyacid anion directionally arranged and evenly dispersed ionic liquid covalently modified polyacid intercalated hydrotalcite. The invention utilizes the characteristics of rich hydroxyl and limited space of hydrotalcite to realize immobilization of ionic liquid and polyacid, and improves the thermal stability and recycling rate of polyacid. covalent modification of the ionic liquid to the hydrotalcite plate not only promote the contact of a desulfurization substrate and catalytic active components in the desulfurization process, but also can avoid additional adding of ionic liquid in each desulfurization process.
Description
Technical field
The invention belongs to technical field of inorganic composite material preparation, particularly to a kind of polyacid of ionic liquid covalent modification
Intercalated houghite and its application in oil product deep desulfuration.
Background technology
Hydrotalcite intercalation structure material (LDHs) is by positively charged main layer board and interlayer anion meridian genomics
The compound filling and being formed.The chemical composition of hydrotalcite intercalation structure material (LDHs) has below formula：[M1-x 2+Mx 3+
(OH)2]x+(An-)x/n·mH2O, wherein M2+And M3+It is respectively divalence and trivalent metal cation, in main layer board；An-For
Interlayer anion；X is M3+/(M2++M3+) molar ratio；M is the number of interlayer hydrone.LDHs has main layer board metal
Ion forms adjustable denaturation, main layer board charge density and its adjustable denaturation of distribution, intercalant anion guest species and quantity can
Denaturation that modulation, inner layer space are adjustable, host-guest interaction the is adjustable design feature such as denaturation, this allows for LDHs and has becoming
The potentiality of outstanding catalyst carrier.
Polyoxometallate (polyacid) is the orderly oxygen of the transition metal such as V, Mo, W and Nb that a big class contains highest valence state
Cluster compound, is a class polynuclear complex.Polyacid has the property such as acidity, oxidation-reduction quality, large scale, high negative electrical charge and compatibility
Matter.These characteristics of polyacid make it play huge effect in each field such as electrochemistry, photochemistry, pharmaceutical chemistry and catalysis.?
In the various applications of polyacid compound, catalysis occupies very important status.Polyacid compound in homogeneous and heterogeneous system,
Can be used as the soda acid of excellent performance, redox or bifunctional catalyst.Rare earth element introducing polyoxoanion is constructed
There is the rare earth polyacid complex of novel structure, have been assigned special optics, magnetics and catalytic performance, there is higher selection
Property and activity, are good catalyst.Rare earth polyacid complex can be realized under relatively mild conditions to gasoline and diesel oil combustion
Sulfur-containing compound ground removing in material, and there is good selectivity and efficiency.At present, a series of hydrogen peroxide/rare earth polyacid is joined
Compound system is used for catalytic desulfurization, shows excellent catalytic performance.
Ionic liquid is the organic liquid material being composed entirely of ions under room temperature and adjacent temperature.Ionic liquid is excellent
Good organic solvent, resolvability polarity, nonpolar organic matter, inorganic substances, have and be easy to separate with other materials, can
The good characteristic such as to recycle.The key feature of ionic liquid is that its property can select anion, cation by suitable
And its substituent and change, you can to design ionic liquid to a certain extent.Ionic liquid is non-volatile, has explosion-proof, can
Reclaim and be easily handled, be described as green solvent.Existing report shows, ionic liquid can extract from gasoline and diesel fuel
Take armaticity sulfur-nitrogen compound, and compared with traditional solvent, they show preferably desulfurized effect.
Hydrotalcite intercalation structure material (LDHs) is a kind of multi-functional anionic type laminated material, and the anion of its interlayer can
Functional polyoxoanion, by design, can be passed through coprecipitation, ion-exchange, calcine-recovering method, layer by layer group by modulation
The method such as dress method and spontaneous flocculence introduces hydrotalcite layers and forms the anionic intercalation configuration material with different performance.Water
The hydroxyl of the ordered arrangement having on talcum laminate can be acted on other organic groups, forms the neatly that special groups are modified
Stone.Have been reported that show can be by ionic liquid covalent modification to hydrotalcite lamina surface, and ionic liquid covalent modification is many
The assembled material of sour intercalated houghite does not also have been reported that so far.
Content of the invention
The purpose of the present invention is by between the neatly stone veneer of rare earth polyacid intercalation to ionic liquid covalent modification, forms ion
The polyacid intercalation hydrotalcite of liquid covalent modification is simultaneously applied to the deep desulfuration of oil product.
The technical scheme is that：Prepare hydrotalcite precursor first and peeled off formation colloid with formamide solution
Solution；Then by covalent modification, ionic liquid is bonded on the hydrotalcite nano lamella of stripping；Recycle rare earth polyacid with
The ordered fabrication of the electrostatic interaction of hydrotalcite nano lamella, forms rare earth polyacid anion and aligns and homodisperse ion
The polyacid intercalation hydrotalcite of liquid covalent modification.
The chemical general formula of the polyacid intercalation hydrotalcite of ionic liquid covalent modification of the present invention is [Mg2+ 1-xAl3+ x
(OH)y(B)2-y]x+(EuW10 9-)x/9MH2O, wherein Mg2+And Al3+In hydrotalcite main layer board, B is covalent modification in water
Ionic liquid 1- octyl group -3- (3- triethoxysilylpropyl) in talcum main layer board -4,5- dihydroxy imidazoles phosphorus hexafluoride, x
For Al3+/(Mg2++Al3+) molar ratio, 0.2≤x≤0.33,0.5≤y≤1.5, m be interlayer hydrone number, m=3-
6.
The preparation process of the polyacid intercalation hydrotalcite of ionic liquid covalent modification of the present invention is as follows：
1) prepare the hydrotalcite precursor that interlayer is nitrate anion；
2) by step 1) be obtained 0.05-0.15g interlayer be nitrate anion hydrotalcite precursor under inert gas shielding
Carry out the stripping reaction of 24-36h in the formamide solution of 100mL, the solution after peeling off is centrifuged, takes its supernatant to obtain
Colloidal solution to clear；
3) to step 2 under inert gas shielding) in colloidal solution add 0.2-0.6g ionic liquid, stir under room temperature
The Na of 0.2-0.6g is added after mixing reaction 24-36h9EuW10·32H2O, reacts 12-36h, and the precipitate with deionized water obtaining is washed
Wash to neutrality, 5-20h is dried in 60-70 DEG C, obtain the polyacid intercalation hydrotalcite of ionic liquid covalent modification.
Described interlayer is that the preparation method of the hydrotalcite precursor of nitrate anion is：
A. magnesium nitrate and aluminum nitrate are dissolved in formation mixing salt solution, the mol ratio of magnesium nitrate and aluminum nitrate in deionized water
For 2-6, the concentration of magnesium nitrate is 0.1-1M；To in mixing salt solution add hexa, hexa mole
Number is 2-6 times of mole summation of magnesium nitrate and aluminum nitrate, and the hydro-thermal then carrying out 12-36h under the conditions of 120-140 DEG C is anti-
Should, the precipitate with deionized water obtaining is washed to neutrality, and 60-70 DEG C is dried 5-20h, obtains the water that interlayer anion is carbonate
Talcum；
B. the hydrotalcite being carbonate by the interlayer anion of the 1g of preparation in step A is scattered under inert gas shielding
In the methanol solution of 100-500mL, after dispersion 3-5h under room temperature, drip red fuming nitric acid (RFNA) 0.5-2.5mL, molten with methyl alcohol after reaction 3-5h
Liquid washs to neutrality, 12h is dried in 60-70 DEG C, obtains the hydrotalcite precursor that interlayer is nitrate anion.
Described ionic liquid is 1- octyl group -3- (3- triethoxysilylpropyl) -4,5- dihydroxy imidazoles phosphorus hexafluoride.
The polyacid intercalation hydrotalcite of the ionic liquid covalent modification of above-mentioned preparation is applied to the depth of oil product as catalyst
Degree desulphurization reaction.Its specific operating condition is：By the polyacid intercalation hydrotalcite of ionic liquid covalent modification, oil product and hydrogen peroxide
It is placed in reaction vessel, the desulfurization substrate in oil product and the mol ratio of the polyacid intercalation hydrotalcite of ionic liquid covalent modification are 4-
16, the mol ratio of the desulfurization substrate in hydrogen peroxide and oil product is 3-5, and reaction temperature is 30-70 DEG C, and the reaction time is 0.5-
2.5h.
It is an advantage of the current invention that：The hydrotalcite that the present invention achieves rare earth polyacid and ionic liquid covalent modification first is received
The intercalation assembling of rice lamella, the hydroxyl being enriched using hydrotalcite and the feature of confinement space realize the immobilized of ionic liquid and polyacid
Change, improve heat endurance and the recovery utilization rate of polyacid, for solution ionic liquid and polyacid during Industrial Catalysis
Recycling has practical significance.This preparation method is simple, workable.By ionic liquid covalent modification to neatly stone veneer
On not only promote the contact with catalytic active component for the desulfurization substrate in sweetening process, and each sweetening process China and foreign countries can be avoided
Plus ionic liquid, and at a temperature of 70 DEG C, in 25min, reach the effect of 99.9% desulfurization.
Brief description
Fig. 1. for FT-IR collection of illustrative plates, wherein, a is ionic liquid 1- octyl group -3- (the 3- triethoxysilicane third that embodiment 1 uses
Base) -4,5- dihydroxy imidazoles phosphorus hexafluoride；B is the hydrotalcite precursor [Mg of nitrate anion for interlayer anion3Al(OH)8]NO3；
C is monomer polyacid Na that embodiment 1 uses9EuW10·32H2O；The polyacid of the ionic liquid covalent modification that d obtains for embodiment 1
Intercalated houghite.
Specific embodiment
Embodiment 1：
A. take 0.03mol Mg (NO3)2·6H2O、0.01mol Mg(NO3)2·6H2O mixes, and is dissolved in 80mL deionized water
In, then take 0.01mol hexamethylenetetramine to add in above-mentioned mixing salt solution, it is centrifuged 10min under 3600rpm/min, take thereon
Clear liquid is transferred in autoclave, hydrothermal crystallizing 24h at 140 DEG C, then filtering and washing, and obtaining interlayer anion is carbonate
Hydrotalcite precursor [Mg3Al(OH)8]CO3.
B. take the [Mg of 1g3Al(OH)8]CO3It is scattered in 100mL methanol solution, be passed through inertia protection gas agitating 3-5h, will
The red fuming nitric acid (RFNA) of 0.5mL adds in dispersion, stirs 3-5h, and reaction is washed to neutrality after terminating, and obtaining interlayer anion is nitre
Hydrotalcite precursor [the Mg of acid group3Al(OH)8]NO3.
C. take the [Mg of 0.1g3Al(OH)8]NO3, stirred in 100mL formamide solvent under the conditions of inertia shielding gas
Mix 24h, the hydrotalcite solution centrifugal after peeling off discards precipitation and obtains clear colloidal solution.
D. under the conditions of inertia shielding gas, by ionic liquid 1- octyl group -3- (3- triethoxysilylpropyl) -4,5- of 0.5g
Dihydroxy imidazoles phosphorus hexafluoride adds in the clear colloidal solution that step c obtains, and stirring reaction 24h adds 0.5g's
Na9EuW10·32H2O, stirring reaction 24h, centrifuge washing, to neutral, is dried to obtain the polyacid intercalation of ionic liquid covalent modification
Hydrotalcite [Mg0.75Al0.25(OH)1.5(C14H28N2O3Si)0.5][EuW10]1.25/453H2O.
Catalytic reaction embodiment 1：
This catalytic reaction is carried out in the simple glass reactor with magnetic agitation.Weigh 90mg embodiment 1 to prepare
Ionic liquid covalent modification polyacid intercalation hydrotalcite as catalyst, add simulation oil (the wherein desulfurization substrate of 5mL afterwards
Sulphur concentration be 1000ppm) and 0.080mL 30wt% hydrogen peroxide, at 70 DEG C reaction, at interval of 5 minutes from reactant
Extract sample in system, using gas chromatographic analysis, calculate the removal efficiency of sulfur-bearing substrate.
Catalytic result is as shown in table 1, as it can be seen from table 1 the polyacid of the ionic liquid covalent modification of embodiment 1 preparation is inserted
99.9% 4,6- dimethyl Dibenzothiophene oxidation can be formed 4,6- dimethyl dibenzo in 25 minutes by layer hydrotalcite
Thiophene sulfone, thus reach significant removal effect.
Table 1：
Claims (6)
1. a kind of polyacid intercalation hydrotalcite of ionic liquid covalent modification is it is characterised in that its chemical general formula is [Mg2+ 1-xAl3+ x
(OH)y(B)2-y]x+(EuW10 9-)x/9MH2O, wherein Mg2+And Al3+In hydrotalcite main layer board, B is covalent modification in water
Ionic liquid 1- octyl group -3- (3- triethoxysilylpropyl) in talcum main layer board -4,5- dihydroxy imidazoles phosphorus hexafluoride, x
For Al3+/(Mg2++Al3+) molar ratio, 0.2≤x≤0.33,0.5≤y≤1.5, m be interlayer hydrone number, m=3-
6.
2. a kind of preparation method of the polyacid intercalation hydrotalcite of ionic liquid covalent modification it is characterised in that its concrete steps such as
Under：
1) prepare the hydrotalcite precursor that interlayer is nitrate anion；
2) by step 1) be obtained 0.05-0.15g interlayer be nitrate anion hydrotalcite precursor under inert gas shielding
Carry out the stripping reaction of 24-36h in the formamide solution of 100mL, the solution after peeling off is centrifuged, takes its supernatant to obtain
The colloidal solution of clear；
3) to step 2 under inert gas shielding) in colloidal solution add the ionic liquid of 0.2-0.6g, stir anti-under room temperature
The Na of 0.2-0.6g is added after answering 24-36h9EuW10·32H2O, react 12-36h, the precipitate with deionized water obtaining wash to
Neutrality, is dried 5-20h in 60-70 DEG C, obtains the polyacid intercalation hydrotalcite of ionic liquid covalent modification.
3. preparation method according to claim 2 is it is characterised in that described interlayer is the hydrotalcite precursor of nitrate anion
Preparation method be：
A. magnesium nitrate and aluminum nitrate are dissolved in formation mixing salt solution in deionized water, the mol ratio of magnesium nitrate and aluminum nitrate is 2-
6, the concentration of magnesium nitrate is 0.1-1M；Add hexa in mixing salt solution, the molal quantity of hexa is
2-6 times of mole summation of magnesium nitrate and aluminum nitrate, then carries out the hydro-thermal reaction of 12-36h under the conditions of 120-140 DEG C, obtains
To precipitate with deionized water wash to neutrality, 60-70 DEG C is dried 5-20h, obtain interlayer anion be carbonate hydrotalcite；
B. the hydrotalcite being carbonate by the interlayer anion of the 1g of preparation in step A is scattered in 100- under inert gas shielding
In the methanol solution of 500mL, drip red fuming nitric acid (RFNA) 0.5-2.5mL after dispersion 3-5h under room temperature, washed with methanol solution after reaction 3-5h
Wash to neutrality, 12h is dried in 60-70 DEG C, obtain the hydrotalcite precursor that interlayer is nitrate anion.
4. preparation method according to claim 2 is it is characterised in that described ionic liquid is 1- octyl group -3- (3- tri- second
Epoxide silicon propyl group) -4,5- dihydroxy imidazoles phosphorus hexafluoride.
5. the polyacid intercalation hydrotalcite of the ionic liquid covalent modification being prepared according to the arbitrary described method of claim 2-4
As application in the deep desulfuration reaction of oil product for the catalyst.
6. application according to claim 5 is it is characterised in that the concrete operations condition of described deep desulfuration reaction is：
The polyacid intercalation hydrotalcite of ionic liquid covalent modification, oil product and hydrogen peroxide are placed in reaction vessel, the desulfurization bottom in oil product
The mol ratio of the polyacid intercalation hydrotalcite of thing and ionic liquid covalent modification is 4-16, the desulfurization substrate in hydrogen peroxide and oil product
Mol ratio is 3-5, and reaction temperature is 30-70 DEG C, and the reaction time is 0.5-2.5h.
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Cited By (8)
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| CN108160110A (en) * | 2017-11-16 | 2018-06-15 | 北京化工大学 | Amphipathic catalysis material, preparation method and the application for being catalyzed brain text reaction grid of ionic liquid covalent modification magnalium hydrotalcite |
| CN108636400A (en) * | 2018-04-28 | 2018-10-12 | 东北师范大学 | A kind of hydrotalcite composite catalyst and its preparation method and application |
| CN111204782A (en) * | 2020-01-19 | 2020-05-29 | 中国科学院宁波材料技术与工程研究所 | Nitrite intercalation hydrotalcite material, aqueous resin composite coating and preparation method thereof |
| CN111875492A (en) * | 2020-05-19 | 2020-11-03 | 北京化工大学 | Preparation method of organic acid anion intercalated hydrotalcite |
| CN112844478A (en) * | 2021-01-04 | 2021-05-28 | 北京化工大学 | Preparation method and application of chiral two-dimensional material based on polyacid intercalation layered silicate |
| CN113493225A (en) * | 2021-08-11 | 2021-10-12 | 洛阳理工学院 | Preparation method and application of Co/Fe layered double-metal hydroxide nanosheets |
| CN114130428A (en) * | 2021-10-27 | 2022-03-04 | 河南大学 | Preparation method and application of novel polyacid-based ionic liquid oxidation desulfurization catalyst |
| CN116371464A (en) * | 2023-02-10 | 2023-07-04 | 华东师范大学 | Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application |
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| CN108160110A (en) * | 2017-11-16 | 2018-06-15 | 北京化工大学 | Amphipathic catalysis material, preparation method and the application for being catalyzed brain text reaction grid of ionic liquid covalent modification magnalium hydrotalcite |
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| CN108636400A (en) * | 2018-04-28 | 2018-10-12 | 东北师范大学 | A kind of hydrotalcite composite catalyst and its preparation method and application |
| CN111204782A (en) * | 2020-01-19 | 2020-05-29 | 中国科学院宁波材料技术与工程研究所 | Nitrite intercalation hydrotalcite material, aqueous resin composite coating and preparation method thereof |
| CN111875492B (en) * | 2020-05-19 | 2023-03-21 | 北京化工大学 | Preparation method of organic acid anion intercalated hydrotalcite |
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| CN112844478A (en) * | 2021-01-04 | 2021-05-28 | 北京化工大学 | Preparation method and application of chiral two-dimensional material based on polyacid intercalation layered silicate |
| CN112844478B (en) * | 2021-01-04 | 2023-05-26 | 北京化工大学 | Preparation method and application of chiral two-dimensional material based on polyacid intercalation layered silicate |
| CN113493225A (en) * | 2021-08-11 | 2021-10-12 | 洛阳理工学院 | Preparation method and application of Co/Fe layered double-metal hydroxide nanosheets |
| CN113493225B (en) * | 2021-08-11 | 2023-11-10 | 洛阳理工学院 | Preparation method and application of Co/Fe layered double hydroxide nanosheets |
| CN114130428A (en) * | 2021-10-27 | 2022-03-04 | 河南大学 | Preparation method and application of novel polyacid-based ionic liquid oxidation desulfurization catalyst |
| CN114130428B (en) * | 2021-10-27 | 2022-12-30 | 河南大学 | Preparation method and application of novel polyacid-based ionic liquid oxidation desulfurization catalyst |
| CN116371464A (en) * | 2023-02-10 | 2023-07-04 | 华东师范大学 | Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application |
| CN116371464B (en) * | 2023-02-10 | 2024-05-17 | 华东师范大学 | Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application |
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