CN106140239A - A kind of polyacid base supported catalyst for desulfurizing oil and preparation method thereof - Google Patents
A kind of polyacid base supported catalyst for desulfurizing oil and preparation method thereof Download PDFInfo
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- CN106140239A CN106140239A CN201510194412.8A CN201510194412A CN106140239A CN 106140239 A CN106140239 A CN 106140239A CN 201510194412 A CN201510194412 A CN 201510194412A CN 106140239 A CN106140239 A CN 106140239A
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Abstract
A kind of to polyacid loaded catalyst with good removal effect of the sulfur-containing compound in oil product and preparation method thereof, belong to technical field of function materials.This material is for γ-Al by amido modified2O3, boehmite and SiO2Doping type γ-Al2O3Or one of which is carrier, obtained, its preparation method by dipping method load polyacid: make carrier react with the active chemical agent containing 3-aminopropyl-groups under inert atmosphere, amino group on carrier surface covalent bonding.Through washing, the process that is dried, soaks in dilute acid soln so that carrier surface becomes positively charged lotus.Afterwards, by carrier in polyacid aqueous solution soaking, washing, dried, i.e. obtain catalyst POMs-NH2-Al2O3.This catalyst for oxidation sweetening reaction not only catalysis oxidation efficiency high, reusable, cheap, and because of its good mechanical performance, separate, reclaim, reuse very convenient.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to a kind of sulfur-containing compound in oil product to be had
Polyacid base supported catalyst of good removal effect and preparation method thereof.
Background technology
Fuel desulfuration technology becomes current as the current Main Means reducing vehicle exhaust sulphur oxide content
Study hotspot.With H2O2Extraction as oxidant combines catalytic oxidation desulfurization oxidative desulfurization techniques and tradition
Hydro desulfurization is compared, have that reaction condition is gentle, desulfurization degree high, corrosivity is little, technique simply, easily grasp
The plurality of advantages such as work, equipment investment is few, operating cost is low, low-carbon energy-saving environmental protection, has become as deep desulfuration
The Main Means of technological development, the catalyst in this catalytic oxidation process plays vital effect undoubtedly.
Conventional catalyst has acetic acid, formic acid and polyacid (POMs) etc., and wherein polyacid such as phosphotungstic acid, phosphomolybdic acid is made
In oxidation sweetening reacts, the highest catalysis activity is shown for catalyst.
But, although heteropoly acid is fine as oxidation sweetening catalysts desulfurized effect, but owing to such is miscellaneous
Polyacid is soluble in the extractants such as acetonitrile, therefore there is the problem that cannot be directly separated recovery.Solve this
The way of problem is by such loaded by heteropoly acid to the carrier with large specific surface area, the most not only can increase
Heavy load is the specific surface area of polyacid on carrier, strengthens its catalytic capability in oxidative desulfurization techniques, and
The most important thing is that making catalyst be easy to separation and recovery reuses.
In numerous carriers, aluminium oxide (ZL 200610114072, ZL201110116418.5, CN 1958456
A, CN103172097A, ZL 200910084540.1, ZL 200610114073.9, CN 103962171A,
ZL 200810226494.X, CN 101543778A, CN 100431965C) owing to having good physics
Chemical property and be widely used in industry.Polyacid is carried on alumina support (POMs@Al at present2O3)
Preparation method mainly have infusion process and a step sol-gal process.When wherein synthesizing with infusion process, polyacid and load
The adhesion of body aluminium oxide is more weak and easy solution-off in polar solvent, it is impossible to reuse；And coagulate with colloidal sol
Polyacid is carried in alumina support by glue method, and polyacid can be decomposed because of the strong basicity of alumina carrier surface,
Lose catalysis activity.
For solving POMs@Al2O3In use easily run off and polyacid is easily decomposed and is difficult to use in industry
The problem that metaplasia is produced, we use first 3-aminopropyl functional group on alumina support bonding, make aluminium oxide ammonia
Base functionalization, on this basis by dipping method load P OMs, has obtained POMs-NH2-Al2O3Catalysis
Agent.POMs-NH2-Al2O3Not only maintain the high-specific surface area that alumina support has, good pore structure,
The advantages such as high mechanical properties and outstanding chemical stability, additionally it is possible to reach following several big purpose: 1, amino is repaiied
The alumina support of decorations can be combined with ionic bond with POMs after being acidified through persalt, solves support type
Catalyst the most easily holds the problem that the separation of flow is lost；2, alumina catalyst support utilize amido modified after,
Avoid and contact with the direct of POMs, the alkalescence on the structure not oxidized aluminum surface of POMs can be kept to break
Bad；3, the aluminium oxide used by the present invention be spherical, bar shaped, column, cellular, lamellar, leafy grass shape or
One therein, spherical particle diameter is 0.05～5mm, a length of the 1 of bar shaped～20cm so that it is be easier to
Separation and recovery, catalyst just can be reclaimed after terminating by reaction with decantation.
Summary of the invention
The purpose of the present invention is to have been proven that polyacid has superior catalytic oxidative to oxidation sweetening process
On the basis of energy, provide a kind of means for solving the actual application of catalyst material: i.e. provide a kind of preparation method
Simply, low cost, stability is high, the oxidation sweetening to oil of good mechanical property has high catalytic activity and
Base supported aluminium oxide catalyst of POMs of reusability and preparation method thereof.
A kind of polyacid base supported catalyst that oil product is had good oxidation desulfurized effect, it is characterised in that
The carrier of this catalyst is γ-Al2O3, boehmite, SiO2Doping type γ-Al2O3Or one therein.
Described Al2O3Carrier surface rich in hydroxyl there is active chemical reactivity, by this surface by change
Learn the response key 3-aminopropyl-groups that closes and realize Al2O3The amination of carrier surface, then acidification,
The carrier surface load after modification of the rear infusion process has the polyacid of good catalytic oxidation desulfurization performance: Keggin
Type polyacid HnXM12-mM’mO40；Dawson type polyacid HnX2M18O62；Anderson type polyacid
HnXO6M6O18Or HnX(OH)6M6O18；Waugh type polyacid HnXM9O32；Silverton type polyacid
HnXM12O42；Vindqvist type polyacid HnM6O19(wherein X=P, Si, Ge, As, S or H, M
=Mo or W, M '=V or Nb).
POMs provided by the present invention is carried on amido modified hydroxyl surface composite to be had oxidation sweetening
There are catalytic efficiency height, mechanical strength good, can again follow through simple process after completing a catalytic reaction
Ring uses, and the development further for oxidative desulfurization techniques provides possibility, is also the industrial applications of POMs
Lay a good foundation.
Accompanying drawing explanation
Fig. 1 embodiment 1 empty Al2O3(curve a), amido modified aluminium oxide NH2-Al2O3(curve b)
With catalyst HPW-NH2-Al2O3(the infrared spectrum comparison diagram of curve c)
In Fig. 2 embodiment 1 catalyst amount be 60mg, oil ratio be 8: 1,60 DEG C of conditions of reaction temperature
Under, the liquid-phase chromatographic analysis figure that in reaction solution, the peak area of DBT changed with the catalytic reaction time
Fig. 3. in embodiment 1 oil ratio be 8: 1, reaction temperature 60 DEG C time different catalysts consumption under with reaction time
Between extend the change curve of desulfuration efficiency；
Fig. 4. in embodiment 1, the catalytic efficiency bar diagram of 5 times reused by catalyst.
Detailed description of the invention
3-aminopropyl triethoxysilane used in following embodiment, 3-aminopropyl trimethoxysilane, phosphorus
Wolframic acid, silico-tungstic acid, normal octane, dibenzothiophenes, toluene, dehydrated alcohol are commercial goods.Wherein first
Benzene and dehydrated alcohol are dried except water processes with standard method before use.Carrier uses front 150～300 DEG C of horses
Not kiln roasting 1～5h.
Embodiment 1
(1) in 50mL three neck round bottom flask, γ-Al pretreated for about 0.8g is put into2O3It is dried with 25mL
Toluene, under nitrogen atmosphere add 0.75mL 3-aminopropyl triethoxysilane, heated and stirred backflow 24h；
(2) γ-Al after processing in step (1) is taken out2O3Bead, at N2Freshly prepd dehydrated alcohol is used under atmosphere
Washing 10h, takes out γ-Al2O3Bead is dried 12h in the thermostatic drying chamber of 80 DEG C, obtains amido modified
γ-Al2O3, it is designated as NH2-Al2O3；
(3) by the NH of preparation in step (2)2-Al2O3Join in the dilute hydrochloric acid solution of pH=4.0, soak
Take out bead after 4h and be at room temperature vacuum dried.
(4) weigh 0.2g phosphotungstic acid and be made into phosphotungstic acid aqueous solution, add the NH processed through step (3)2-Al2O3
Bead, takes out bead and is washed with deionized three times after soaking 4h, each 10mL, and ambient temperature in vacuum is dried,
Obtain catalyst, be designated as HPW-NH2-Al2O3。
Embodiment 2
(1) in 50mL three neck round bottom flask, γ-Al pretreated for about 0.8g is put into2O3It is dried with 25mL
Toluene, under nitrogen atmosphere add 0.75mL 3-aminopropyl trimethoxysilane, heated and stirred backflow 24h；
(2) γ-Al after processing in step (1) is taken out2O3Bead, at N2Freshly prepd dehydrated alcohol is used under atmosphere
Washing 10h, takes out γ-Al2O3Bead is dried 12h in the thermostatic drying chamber of 80 DEG C, obtains amido modified
γ-Al2O3, i.e. NH2-Al2O3；
(3) by the NH of preparation in step (2)2-Al2O3Join in the dilute hydrochloric acid solution of pH=4.0, soak
Take out bead after 4h and be at room temperature vacuum dried.
(4) weigh 0.2g silico-tungstic acid and be made into silicon tungsten acid solution, add the NH processed through step (3)2-Al2O3
Bead, takes out bead and is washed with deionized three times after soaking 4h, each 10mL, and ambient temperature in vacuum is dried,
Obtain catalyst, be designated as HSiW-NH2-Al2O3。
Embodiment 3
(1) in 50mL three neck round bottom flask, the siliceous Al of about 0.8g is put into2O3(it is designated as SiO2@Al2O3)
The toluene being dried with 25mL, adds 0.75mL 3-aminopropyl triethoxysilane under nitrogen atmosphere, heating is stirred
Mix backflow 24h；
(2) SiO after processing in step (1) is taken out2@Al2O3, at N2Freshly prepd dehydrated alcohol is used under atmosphere
Washing 10h, takes out SiO2@Al2O3In the thermostatic drying chamber of 80 DEG C, it is dried 12h, obtains amido modified
γ-Al2O3, i.e. NH2-SiO2@Al2O3；
(3) by the NH of preparation in step (2)2-SiO2@Al2O3Join in the dilute hydrochloric acid solution of pH=4.0,
Take out bead after soaking 4h and be at room temperature vacuum dried.
(4) weighing 0.2g phosphotungstic acid and be made into phosphotungstic acid aqueous solution, addition processes through step (3)
NH2-SiO2@Al2O3Bead, takes out bead and is washed with deionized three times after soaking 4h, each 10mL,
Ambient temperature in vacuum is dried, and i.e. obtains catalyst HPW-NH2-SiO2@Al2O3。
Test HPW-NH in embodiment 12-Al2O3Catalyst, blank Al2O3With amido modified aluminium oxide
NH2-Al2O3Infrared spectrum (Fig. 1) and HPW-NH2-Al2O3Catalyst is to sulfur-containing compound in simulated oil
The catalytic oxidative desulfurization performance (Fig. 2, Fig. 3, Fig. 4) of dibenzothiophenes.
HPW-NH2-Al2O3Catalyst is to the catalytic oxidative desulfurization of sulfur-containing compound dibenzothiophenes in simulated oil
Performance test, specifically comprises the following steps that and burns to the 100mL tri-neck round bottom equipped with thermometer, condensing tube and rotor
In Ping, (sulfur content is 350ppmw for addition 20mL normal octane and 0.0406g DBTs), add 20mL second
Nitrile, as extractant, heats in the water-bath of 60 DEG C.Respective amount put into by the catalyst weighing certain mass
30%H2O2In solution, after the solution in three-necked bottle reaches 60 DEG C, by containing of preparation
HPW-NH2-Al2O3The H of catalyst2O2Solution is poured into and is carried out catalytic desulfurization reaction in three-necked bottle.
Under conditions of catalytic amount, oil ratio are identical with reaction temperature, along with the prolongation DBT in response time
Peak area be gradually reduced (Fig. 2), the prolongation along with the response time is described, the residual volume of DBT gradually decreases,
I.e. desulfurization degree increases.In the case of oil ratio is identical with reaction temperature, different catalysts is along with the response time
Extending the change of desulfurization degree, find along with catalyst amount and the increase in response time, desulfuration efficiency is the most gradually
Increase reaction, show that optimum catalyst consumption is 60mg and Best Times is 2h (Fig. 3).
By HPW-NH2-Al2O3In optimum experimental condition (catalyst amount 60mg, oil ratio 8: 1, reaction
Temperature 60 C, response time 2h) under, investigate the repeat performance of this catalyst, often complete once to urge
After changing desulphurization reaction, catalyst reuses after simple toluene and dried, is repeated 5 times, de-
Sulphur efficiency is reduced to 98.6% (Fig. 4) by 99.2% when using for the first time, illustrates that this catalyst has preferably
Repeat performance.
Claims (8)
1. the catalyst that oil product is had good oxidation desulfurized effect, it is characterised in that this catalyst be by
The polyacid of polyacid component and the surface carrier composition through modifying with good oxidation catalysis activity is base supported
Catalyst.
Polyacid base supported catalyst preparation method the most according to claim 1, it is characterised in that with oxidation
Aluminum is carrier, comprises the following steps:
(1) 0.5～2.0g carrier is joined in the 20～100mL toluene being dried, add under an inert atmosphere
0.5～the 2.0mL chemical reagent processed for carrier surface amino functional, stirs and is heated to reflux 18～24
Hour；
(2) reacted carrier is taken out, wash under an inert atmosphere with dehydrated alcohol 8～20 hours, in 80
～be dried at 100 DEG C；
(3) dried carrier is joined and the dilute acid soln that pH is 2～6 soaks acidifying in 4～8 hours,
Take out and dried；
(4) it is 10: 0.1～10: 5 polyacid to be made into aqueous solution by carrier and polyacid mass ratio, soaks above-mentioned process
After carrier 4～after 8 hours, take out and be washed with deionized 3～5 times, the most i.e. obtain many acidic groups
Loaded catalyst.
Polyacid base supported catalyst preparation method the most according to claim 2, it is characterised in that used
Alumina support is γ-Al2O3, boehmite and SiO2Doping type γ-Al2O3Or one therein.
Polyacid base supported catalyst preparation method the most according to claim 2, it is characterised in that used
Alumina support is spherical, bar shaped, column, cellular, lamellar or leafy grass shape, and spherical particle diameter is 0.05
～5mm, a length of the 0.1 of bar shaped～20cm.
Polyacid base supported catalyst preparation method the most according to claim 2, it is characterised in that load used
Surface have passed through amino functional and acidification.
Polyacid base supported catalyst preparation method the most according to claim 2, it is characterised in that many acidic groups
Loaded catalyst is at Al2O3After carrier surface amino functional is modified, then by infusion process, polyacid is loaded
It is prepared from carrier.
Polyacid base supported catalyst preparation method the most according to claim 2, it is characterised in that be used for carrying
The chemical reagent that surface amino functional processes is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxy
Silane, 3-aminopropyl trichlorosilane or one therein；Chemical reagent used by acidification be hydrochloric acid, sulphuric acid,
Hydrobromic acid, phosphoric acid, acetic acid or one therein.
Polyacid base supported catalyst preparation method the most according to claim 2, it is characterised in that used many
Acid is the polyacid with good catalytic oxidation desulfurization performance: Keggin-type polyacid HnXM12-mM’mO40；
Dawson type polyacid HnX2M18O62；Anderson type polyacid HnXO6M6O18Or HnX(OH)6M6O18；
Waugh type polyacid HnXM9O32；Silverton type polyacid HnXM12O42；Vindqvist type polyacid HnM6O19
(wherein X=P, Si, Ge or As, M=Mo or W, M '=V or Nb) or one therein.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108277043A (en) * | 2018-02-26 | 2018-07-13 | 烟台大学 | A kind of method of diesel fuel desulfurization |
| CN109908962A (en) * | 2019-03-04 | 2019-06-21 | 浙江大学宁波理工学院 | The ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid, preparation method and application |
| CN110586186A (en) * | 2019-08-13 | 2019-12-20 | 中北大学 | High-dispersion polyoxometallate magnetic microsphere catalyst and preparation method and application thereof |
| CN110773231A (en) * | 2019-11-27 | 2020-02-11 | 贵州大学 | Preparation method of nano-scale fuel oil catalytic oxidation-adsorption desulfurization catalyst |
| CN111346490A (en) * | 2020-03-18 | 2020-06-30 | 山东大学深圳研究院 | Polyacid-based green desulfurization system, desulfurization-electrochemical regeneration synergistic cyclic desulfurization hydrogen byproduct method, system and application |
| CN113527697A (en) * | 2021-05-31 | 2021-10-22 | 渤海大学 | Waugh type polyoxometallate base metal-organic complex for efficient catalytic oxidation desulfurization and application thereof |
| CN113522356A (en) * | 2021-07-14 | 2021-10-22 | 营口理工学院 | Heterogeneous oxidation desulfurization catalyst and preparation method thereof |
| CN113842948A (en) * | 2021-09-24 | 2021-12-28 | 贵州大学 | Nano phenolic resin-based desulfurization catalyst and preparation method thereof |
| CN114849777A (en) * | 2022-04-25 | 2022-08-05 | 贵州大学 | 2D lamellar structure silicon dioxide-based desulfurization catalyst and preparation method thereof |
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| CN108277043A (en) * | 2018-02-26 | 2018-07-13 | 烟台大学 | A kind of method of diesel fuel desulfurization |
| CN108277043B (en) * | 2018-02-26 | 2019-12-03 | 烟台大学 | A kind of method of diesel fuel desulfurization |
| CN109908962A (en) * | 2019-03-04 | 2019-06-21 | 浙江大学宁波理工学院 | The ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid, preparation method and application |
| CN110586186A (en) * | 2019-08-13 | 2019-12-20 | 中北大学 | High-dispersion polyoxometallate magnetic microsphere catalyst and preparation method and application thereof |
| CN110773231A (en) * | 2019-11-27 | 2020-02-11 | 贵州大学 | Preparation method of nano-scale fuel oil catalytic oxidation-adsorption desulfurization catalyst |
| CN111346490B (en) * | 2020-03-18 | 2022-02-08 | 山东大学深圳研究院 | Polyacid-based green desulfurization system, desulfurization-electrochemical regeneration synergistic cyclic desulfurization hydrogen byproduct method, system and application |
| CN111346490A (en) * | 2020-03-18 | 2020-06-30 | 山东大学深圳研究院 | Polyacid-based green desulfurization system, desulfurization-electrochemical regeneration synergistic cyclic desulfurization hydrogen byproduct method, system and application |
| CN113527697A (en) * | 2021-05-31 | 2021-10-22 | 渤海大学 | Waugh type polyoxometallate base metal-organic complex for efficient catalytic oxidation desulfurization and application thereof |
| CN113527697B (en) * | 2021-05-31 | 2022-10-14 | 渤海大学 | Waugh type polyoxometallate base metal-organic complex for efficient catalytic oxidation desulfurization and application thereof |
| CN113522356A (en) * | 2021-07-14 | 2021-10-22 | 营口理工学院 | Heterogeneous oxidation desulfurization catalyst and preparation method thereof |
| CN113842948A (en) * | 2021-09-24 | 2021-12-28 | 贵州大学 | Nano phenolic resin-based desulfurization catalyst and preparation method thereof |
| CN113842948B (en) * | 2021-09-24 | 2023-05-23 | 贵州大学 | Nano phenolic resin-based desulfurization catalyst and preparation method thereof |
| CN114849777A (en) * | 2022-04-25 | 2022-08-05 | 贵州大学 | 2D lamellar structure silicon dioxide-based desulfurization catalyst and preparation method thereof |
| CN114849777B (en) * | 2022-04-25 | 2023-09-19 | 贵州大学 | 2D lamellar structure silicon dioxide-based desulfurization catalyst and preparation method thereof |
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