CN110180584A - The zeolite molecular sieve support type composite catalyst and preparation method thereof of dibenzothiophenes in a kind of removal oil product - Google Patents
The zeolite molecular sieve support type composite catalyst and preparation method thereof of dibenzothiophenes in a kind of removal oil product Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The invention discloses a kind of zeolite molecular sieve support type composite catalysts and preparation method thereof of dibenzothiophenes in removal oil product, and the composite catalyst is using zeolite molecular sieve as carrier, and load has molybdenum trioxide and titanium dioxide thereon.Preparation method includes preparing zeolite molecular sieve suspension, it is prepared into precursor mixture with tetrabutyl titanate solution, Ammoniun Heptamolybdate Solution；Precursor mixture roast, composite catalyst of the present invention is made.Composite catalyst of the present invention has many advantages, such as that economical and practical, catalytic oxidation performance is good, it is good to recycle performance; it being capable of effective conversion of the realization to sulfur-bearing organic pollutant quickly and efficiently when for removing the sulfur-bearing organic pollutant in oil product; reach ultra high efficiency and ultra-deep oxidation sweetening; there are fabulous economic benefit and application prospect; preparation method has many advantages, such as that simple process, easy to operate, raw material are cheap and easy to get, preparation cost is cheap; the batch preparation that scale can be achieved, is conducive to industrialized utilization.
Description
Technical field
The invention belongs to heterogeneous catalysis technology and its technical field of petrochemical industry, it is related to dibenzo thiophene in a kind of removal oil product
Zeolite molecular sieve support type composite catalyst of pheno and preparation method thereof.
Background technique
In recent decades, the discharge of sulphur organic compound has seriously affected air quality in petroleum, compromises human health,
Shorten the service life of various automobile engines.It is required in the rule of existing clean air highway diesel oil: in highway diesel oil
Sulfur content is 15 mg/litres, and manufacturers of engines is allowed to use the advanced discharge that can be further reduced discharge of poisonous waste
Control system.But the organic matter of these sulfur-bearings can cause corrosion to shorten automotive service life to engine.Therefore, there is an urgent need to look for
These harmful organic compounds containing sulfurs are removed from crude oil to a kind of suitable sulfur method.
Oxidation sweetening (ODS) has many advantages, such as that mild operating condition, (room temperature, normal pressure) easy to operate, desulfuration efficiency are high, quilt
It is considered a kind of green ultra-deep desulfuration technology with bright prospects.The validity of oxidation process, which depends greatly on, urges
Agent high efficiency.In recent years, all searchings of many researchers prepare a kind of oxidation-desulfurizing catalyst haveing excellent performance.It is related to urge
Change petroleum oxidate in organic sulfur compound catalyst there are many report.Such as: metal oxide, metal organic framework (MOF)
The solid phase supported catalysts such as supported catalyst.Solid phase supported catalyst can by filter well and separated from petroleum, because
And solid phase supported catalyst is widely used in catalysis oxidation petroleum sweetening, however, existing solid phase supported catalyst is for being catalyzed
The problems such as higher cost, catalytic oxidation performance are insufficient, regenerability is poor is still had when petroleum oxidate desulfurization, this severely limits
The extensive use of solid phase supported catalyst.In addition, there is system in the preparation method of existing most of solid phase supported catalysts
Standby the problems such as process is comparatively laborious, preparation cost is relatively high, and many transition metal are not easy successfully to be supported on carrier, this is also limited
The practical application of solid phase supported catalyst is made.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of economical and practical, catalysis oxygen
Change performance it is good, recycle performance it is good removal oil product in dibenzothiophenes zeolite molecular sieve support type composite catalyst, also
Dibenzothiophenes in the removal oil product that a kind of simple process, easy to operate, raw material are cheap and easy to get, preparation cost is cheap is provided
The preparation method of zeolite molecular sieve support type composite catalyst.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
The zeolite molecular sieve support type composite catalyst of dibenzothiophenes in a kind of removal oil product, the zeolite molecular sieve are negative
Load type composite catalyst is using zeolite molecular sieve as carrier, and load has molybdenum trioxide and titanium dioxide on the zeolite molecular sieve.
Above-mentioned zeolite molecular sieve support type composite catalyst, further improved, the zeolite molecular sieve support type is multiple
Closing the mass ratio of molybdenum and titanium in catalyst is 1~4: 4~1；Molybdenum and titanium in the zeolite molecular sieve support type composite catalyst
Gross mass is the 20%~25% of zeolite molecular sieve.
Above-mentioned zeolite molecular sieve support type composite catalyst, further improved, institute's zeolite molecular sieve is MCM-22.
The inventive concept total as one, the present invention also provides a kind of boilings of dibenzothiophenes in above-mentioned removal oil product
The preparation method of the molecular sieve carried type composite catalyst of stone, comprising the following steps:
S1, zeolite molecular sieve is made to zeolite molecular sieve suspension；
S2, zeolite molecular sieve suspension, tetrabutyl titanate solution obtained in step S1 and Ammoniun Heptamolybdate Solution are mixed,
Stirring impregnates, and is centrifuged, and drying obtains precursor mixture；
S3, precursor mixture obtained in step S2 is roasted, obtains zeolite molecular sieve support type composite catalyzing
Agent.
Above-mentioned preparation method, it is further improved, it is in the step S2, tetrabutyl titanate solution and ammonium heptamolybdate is molten
Liquid is added drop-wise in zeolite molecular sieve suspension simultaneously；The drop rate of the tetrabutyl titanate solution be 1.5mL/min~
2.5mL/min；The drop rate of the Ammoniun Heptamolybdate Solution is 1.5mL/min~2.5mL/min.
Above-mentioned preparation method, it is further improved, in the step S2, the revolving speed of the stirring be 1000r/min~
2000r/min；The time of the stirring is 2h~4h；The time of the dipping is 20h~30h；The revolving speed of the centrifugation is
5000r/min~6000r/min.
Above-mentioned preparation method, it is further improved, in the step S1, the preparation side of the zeolite molecular sieve suspension
Method the following steps are included:
(1) zeolite molecular sieve is mixed with ammonium nitrate solution, is stirred, cleaned, drying repeats aforesaid operations 2~3 times；
(2) zeolite molecular sieve after drying in step (1) is roasted；
(3) zeolite molecular sieve after roasting in step (2) is mixed, ultrasound, stirring with water, obtains zeolite molecular sieve suspension
Liquid.
Above-mentioned preparation method, it is further improved, in the step (1), the zeolite molecular sieve and ammonium nitrate solution
Ratio be 0.5g: 50mL；The concentration of the ammonium nitrate solution is 1mol/L；The stirring carries out at being 80 DEG C in temperature；Institute
The time for stating stirring is 2h；The drying carries out under vacuum conditions；The temperature of the drying is 80 DEG C；
In the step (2), the heating rate in the roasting process is 5 DEG C/min；The roasting is 550 DEG C in temperature
Lower progress；The time of the roasting is 3h；
In the step (3), the ratio of zeolite molecular sieve and water after the roasting is 0.5g: 50mL；The ultrasound
Time is 30min.
Above-mentioned preparation method, it is further improved, in the step S3, in the roasting process heating rate be 5 DEG C/
min；The roasting carries out at being 550 DEG C in temperature；The time of the roasting is 3h.
Compared with the prior art, the advantages of the present invention are as follows:
(1) the present invention provides it is a kind of removal oil product in dibenzothiophenes zeolite molecular sieve support type composite catalyst,
Using zeolite molecular sieve as carrier, load has molybdenum trioxide and titanium dioxide on zeolite molecular sieve.In the present invention, zeolite molecular sieve with
The advantages that its large specific surface area, stability is good, acidic site abundant is a kind of most suitable carrier.In addition, due to three oxygen
Changing molybdenum and titanium dioxide has many advantages, such as that cheap, nontoxic, thermal stability is high, chemical stability is high, thus by three oxygen
Change molybdenum and titanium dichloride load on zeolite molecular sieve so that the advantages of composite catalyst set the two, have it is low in cost,
Nontoxic, the advantages that thermal stability is high, chemical stability is high.In addition, by molybdenum trioxide and titanium dichloride load in zeolite point
But also composite catalyst shows preferable regenerability on son sieve, be conducive to the recycling property for improving composite catalyst
Energy.Zeolite molecular sieve support type composite catalyst of the present invention is with economical and practical, catalytic oxidation performance is good, it is good to recycle performance
The advantages that, when the sulfur-bearing organic pollutant being used in removal oil product can realization quickly and efficiently it is organic to sulfur-bearing
Effective conversion of pollutant, reaches ultra high efficiency and ultra-deep oxidation sweetening, there is fabulous economic benefit and application prospect.
(2) in zeolite molecular sieve support type composite catalyst of the present invention the mass ratio of molybdenum and titanium be 1~4: 4~1, and molybdenum and
The gross mass of titanium is the 20%~25% of zeolite molecular sieve, wherein the mass ratio of molybdenum and titanium be 1~4: 4~1 refer to molybdenum and titanium this
A ratio between two activated centres, and the gross mass of molybdenum and titanium refers in activity for the 20%~25% of zeolite molecular sieve
The heart accounts for a ratio of carrier, by optimizing the mass ratio and molybdenum titanium gross mass accounting of molybdenum and titanium, further promotes catalyst
Catalytic oxidation performance and regenerability, to obtain better catalytic oxidation effect, realize it is more inexpensive, more efficiently urge
Change oxidation, can convert to high efficiency, low cost the sulfur-bearing organic pollutant in petroleum.
(3) the present invention provides the zeolite molecular sieve support type composite catalysts of dibenzothiophenes in a kind of removal oil product
Preparation method, using zeolite molecular sieve, tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution as raw material, by mixing, stirring by each raw material
It mixes, impregnate, be centrifuged, dry and roast and zeolite molecular sieve support type composite catalyst is made.Preparation method of the present invention has technique
Be simple and convenient to operate, the advantages that raw material are cheap and easy to get, preparation cost is cheap, is, it can be achieved that prepared by the batch of scale, be conducive to work
Industryization utilizes.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is the preparation process flow schematic diagram of zeolite molecular sieve support type composite catalyst in the embodiment of the present invention 1.
Fig. 2 schemes for the TEM of zeolite molecular sieve support type composite catalyst obtained in the embodiment of the present invention 1.
Fig. 3 is different catalysts in the embodiment of the present invention 6 to the changing effect figure of sulphur in dibenzothiophenes.
Fig. 4 is zeolite molecular sieve support type composite catalyst in the embodiment of the present invention 7 to the circulation of sulphur in dibenzothiophenes
Treatment effect figure.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Material employed in following embodiment and instrument are commercially available.
Embodiment 1
The zeolite molecular sieve support type composite catalyst of dibenzothiophenes in a kind of removal oil product is to carry with zeolite molecular sieve
Body, load has molybdenum trioxide and titanium dioxide on zeolite molecular sieve.
In the present embodiment, the mass ratio of molybdenum and titanium is 1: 4 in zeolite molecular sieve support type composite catalyst, and molybdenum and titanium
Gross mass is the 22.10% of zeolite molecular sieve.
In the present embodiment, zeolite molecular sieve MCM-22；Molybdenum trioxide belongs to 210 crystal faces, spacing of lattice 0.345nm；
Titanium dioxide is Detitanium-ore-type, belongs to 101 crystal faces, spacing of lattice 0.352nm.
A kind of preparation method of zeolite molecular sieve support type composite catalyst in the embodiments of the present invention prepares work
Skill flow diagram is as shown in Figure 1, comprising the following steps:
(1) MCM-22 suspension is prepared:
(1.1) MCM-22 is added in the ammonium nitrate solution of 50mL, 1mol/L, 2h, deionized water is stirred at 80 DEG C
It washes three times, is under vacuum conditions to be dried at 80 DEG C in temperature, repeats aforesaid operations twice.
(1.2) it by the MCM-22 grinding in step (1.1) after drying, is placed in temperature programmed control Muffle furnace and is with heating rate
5 DEG C/min is warming up to 550 DEG C of roasting 3h.In the present invention, zeolite molecular sieve is enabled to obtain better stability by roasting.
(1.3) MCM-22 (H-MCM-22) after roasting in 0.5g step (1.2) is added to 50mL deionized water, ultrasound
30min, stirring, obtains MCM-22 suspension.In the present invention, using deionized water as solvent, cost is relatively low.
(2) precursor mixture is prepared:
(2.1) 1.42mL tetrabutyl titanate is added in 5mL dehydrated alcohol, it is molten to obtain tetrabutyl titanate by ultrasonic 30min
Liquid.0.092g ammonium heptamolybdate is added in 5mL deionized water, ultrasonic 30min obtains Ammoniun Heptamolybdate Solution.In the present invention, with titanium
Sour N-butyl has many advantages, such as that hydrolysis rate is moderate, hydrolytic process is controllable, element sulphur free from foreign meter for titanium source, and isopropyl titanate
It is deposited because hydrolysis rate is too fast the problem of should not controlling during the preparation process, titanium sulfate can introduce element sulphur and finally influence catalyst
Using effect.In the present invention, have many advantages, such as that low in cost, preparation efficiency is high using ammonium heptamolybdate as molybdenum source.
(2.2) under the conditions of stirring (revolving speed 1500r/min) by tetrabutyl titanate solution obtained in step (2.1) and
Ammoniun Heptamolybdate Solution is added drop-wise to simultaneously in step (1) in MCM-22 suspension obtained, wherein tetrabutyl titanate solution and seven molybdenums
The drop rate of acid ammonium solution is 2.0mL/min, continues to stir 4h in the case where speed of agitator is 1500r/min after being added dropwise to complete,
Dipping (dipping process is to stand mixed solution) is 5000r/min centrifugation in revolving speed, it is mixed to obtain presoma for drying for 24 hours
Close object.By the drop rate of optimization tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution in the present invention, the positive fourth of metatitanic acid is enabled to
Ester and ammonium heptamolybdate are evenly distributed on MCM-22 carrier, and molybdenum trioxide and titanium dioxide is prepared by subsequent calcination process
Titanium is evenly distributed on the composite catalyst on MCM-22 carrier, this is because drop rate will lead to tetrabutyl titanate solution slowly excessively
Hydrolysis, and too fast will lead to tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution uneven distribution is eventually collected in MCM-22 carrier
On, it is difficult to be evenly distributed on MCM-22 carrier so as to cause the molybdenum trioxide and titanium dioxide generated during subsequent calcination process
On.
(3) zeolite molecular sieve support type composite catalyst is prepared:
It is 5 DEG C/min according to heating rate, precursor mixture obtained in step (2) is warming up to 550 DEG C of roasting 3h,
Obtain zeolite molecular sieve support type composite catalyst, as MoO3-TiO2/ MCM-22, number A1.In the present invention, pass through roasting
On the one hand it is to remove extra moisture and unstable material, i.e., titanium source and molybdenum source is transformed under the high temperature conditions respectively and played
On the other hand the titanium dioxide and molybdenum trioxide product of catalytic action promote the stable structure of catalyst by calcining at high temperature
Property, keep catalyst more stable under subsequent progress oxidation sweetening experimental condition.
Fig. 2 schemes for the TEM of zeolite molecular sieve support type composite catalyst obtained in the embodiment of the present invention 1.It can by Fig. 2
Know, molybdenum trioxide and titanium dioxide are successfully supported on MCM-22, and are supported on the molybdenum trioxide on MCM-22 and titanium dioxide
Titanium has lattice, obtains crystal face type by XRD colorimetric card, obtains spacing of lattice by calculating, the results showed that molybdenum trioxide category
In 210 crystal faces, spacing of lattice 0.345nm；Titanium dioxide is Detitanium-ore-type, belongs to 101 crystal faces, spacing of lattice 0.352nm.
Embodiment 2
The zeolite molecular sieve support type composite catalyst of dibenzothiophenes, the zeolite with embodiment 1 in a kind of removal oil product
Molecular sieve carried type composite catalyst (A1) is essentially identical, and difference is only that: the zeolite molecular sieve support type of embodiment 2 is compound to urge
The mass ratio of molybdenum and titanium is 2: 3 in agent.
A kind of preparation method of zeolite molecular sieve support type composite catalyst, it is essentially identical with the preparation method of embodiment 1,
Difference is only that: tetrabutyl titanate is different with the dosage of ammonium heptamolybdate in the preparation method of embodiment 2.Metatitanic acid is being just in the embodiment
The specific dosage of butyl ester and ammonium heptamolybdate, those skilled in the art can according to molybdenum in zeolite molecular sieve support type composite catalyst and
The mass ratio of titanium is 2: 3, beyond all doubt, unique acquisition.
Zeolite molecular sieve support type composite catalyst obtained, number A2 in embodiment 2.
Embodiment 3
The zeolite molecular sieve support type composite catalyst of dibenzothiophenes, the zeolite with embodiment 1 in a kind of removal oil product
Molecular sieve carried type composite catalyst (A1) is essentially identical, and difference is only that: the zeolite molecular sieve support type of embodiment 3 is compound to urge
The mass ratio of molybdenum and titanium is 1: 1 in agent.
A kind of preparation method of zeolite molecular sieve support type composite catalyst, it is essentially identical with the preparation method of embodiment 1,
Difference is only that: tetrabutyl titanate is different with the dosage of ammonium heptamolybdate in the preparation method of embodiment 3.Metatitanic acid is being just in the embodiment
The specific dosage of butyl ester and ammonium heptamolybdate, those skilled in the art can according to molybdenum in zeolite molecular sieve support type composite catalyst and
The mass ratio of titanium is 1: 1, beyond all doubt, unique acquisition.
Zeolite molecular sieve support type composite catalyst obtained, number A3 in embodiment 3.
Embodiment 4
The zeolite molecular sieve support type composite catalyst of dibenzothiophenes, the zeolite with embodiment 1 in a kind of removal oil product
Molecular sieve carried type composite catalyst (A1) is essentially identical, and difference is only that: the zeolite molecular sieve support type of embodiment 4 is compound to urge
The mass ratio of molybdenum and titanium is 3: 2 in agent.
A kind of preparation method of zeolite molecular sieve support type composite catalyst, it is essentially identical with the preparation method of embodiment 1,
Difference is only that: tetrabutyl titanate is different with the dosage of ammonium heptamolybdate in the preparation method of embodiment 4.Metatitanic acid is being just in the embodiment
The specific dosage of butyl ester and ammonium heptamolybdate, those skilled in the art can according to molybdenum in zeolite molecular sieve support type composite catalyst and
The mass ratio of titanium is 3: 2, beyond all doubt, unique acquisition.
Zeolite molecular sieve support type composite catalyst obtained, number A4 in embodiment 4.
Embodiment 5
The zeolite molecular sieve support type composite catalyst of dibenzothiophenes, the zeolite with embodiment 1 in a kind of removal oil product
Molecular sieve carried type composite catalyst (A1) is essentially identical, and difference is only that: the zeolite molecular sieve support type of embodiment 5 is compound to urge
The mass ratio of molybdenum and titanium is 4: 1 in agent.
A kind of preparation method of zeolite molecular sieve support type composite catalyst, it is essentially identical with the preparation method of embodiment 1,
Difference is only that: tetrabutyl titanate is different with the dosage of ammonium heptamolybdate in the preparation method of embodiment 5.Metatitanic acid is being just in the embodiment
The specific dosage of butyl ester and ammonium heptamolybdate, those skilled in the art can according to molybdenum in zeolite molecular sieve support type composite catalyst and
The mass ratio of titanium is 4: 1, beyond all doubt, unique acquisition.
Zeolite molecular sieve support type composite catalyst obtained, number A5 in embodiment 5.
Comparative example 1
A kind of preparation method of titanium dioxide/zeolite molecular sieve composite catalyst, comprising the following steps: by 1.78mL metatitanic acid
N-butyl adds in 5mL dehydrated alcohol, and ultrasonic 30min obtains tetrabutyl titanate solution.Under the conditions of stirring (1500r/min)
Tetrabutyl titanate solution is added drop-wise in embodiment 1 in MCM-22 suspension obtained with the speed of 2.0mL/min, and continues to exist
Speed of agitator is to stir 4h under 1500r/min, is 5000r/min centrifugation in revolving speed, drying roasts mixture at 550 DEG C
3h obtains titanium dioxide/zeolite molecular sieve composite catalyst, as TiO2/ MCM-22, number B1.
Comparative example 2
A kind of preparation method of molybdenum trioxide/zeolite molecular sieve composite catalyst, comprising the following steps: by 0.4601g seven
Ammonium molybdate adds in 5mL deionized water, and ultrasonic 30min obtains Ammoniun Heptamolybdate Solution.It will under the conditions of stirring (1500r/min)
Ammoniun Heptamolybdate Solution is added drop-wise in embodiment 1 in MCM-22 mixed liquor obtained with the speed of 2.0mL/min, is in speed of agitator
1500r/min stirs 4h, is 5000r/min centrifugation in revolving speed, mixture is roasted 3h at 550 DEG C, obtains three oxidations by drying
Molybdenum/zeolite molecular sieve composite catalyst, as MoO3/ MCM-22, number B2.
Embodiment 6
Investigate influence of the different catalysts to dibenzothiophenes removal effect in oil product, comprising the following steps:
Zeolite molecular sieve support type composite catalyst (A1, A2, A3, A4, A5) obtained, comparative example 1 in Example 1-5
In titanium dioxide/zeolite molecular sieve composite catalyst (B1) obtained, molybdenum trioxide/zeolite molecular sieve obtained in comparative example 2
Composite catalyst (B2), each 0.10g, be added separately to 20mL, containing sulphur concentration be 500ppmw dibenzothiophenes (DBT)-it is just pungent
In alkane solution (the as simulation petroleum containing dibenzothiophenes), it is separately added into 280 μ L, the peroxidating ring that mass fraction is 50%
Hexanone (oxidant, O/S=2) solution reacts 30min in the oil bath pan that temperature is 100 DEG C under magnetic agitation, completes to stone
The removal of dibenzothiophenes in oil product.
It is cooled to room temperature after the reaction was completed, the content of sulphur in dibenzothiophenes in products therefrom solution is reacted in measurement, and is led to
The conversion ratio for calculating and obtaining sulphur in dibenzothiophenes is crossed, as a result as shown in Figure 3；Meanwhile it will be in fixed reaction products therefrom solution
Catalyst is separated by filtration with simulation petroleum (normal octane), further, separating obtained simulation petroleum is moved in separatory funnel, is added
The n,N-dimethylacetamide extraction for entering 10mL is primary, takes upper oil phase after layering is obvious；With gas chromatographic detection upper oil phase
The content of middle sulphur.
Fig. 3 is different catalysts in the embodiment of the present invention 6 to the changing effect figure of sulphur in dibenzothiophenes.From the figure 3, it may be seen that
Zeolite molecular sieve support type composite catalyst (A1, A2, A3, A4, A5) produced by the present invention can effectively convert in oil product
Dibenzothiophenes, wherein zeolite molecular sieve support type composite catalyst (A1, A2, A3, A4, A5) is to sulphur in dibenzothiophenes
Conversion ratio is respectively 100%, 91.54%, 85.83%, 83.84%, 83.05%, and titanium dioxide obtained in comparative example 1/
Molybdenum trioxide/zeolite molecular sieve composite catalyst (B2) obtained is to two in zeolite molecular sieve composite catalyst (B1), comparative example 2
The conversion ratio of sulphur is respectively 58.64% and 36.43% in benzothiophene.The above result shows that the present invention is simultaneously by molybdenum trioxide
With titanium dichloride load on zeolite molecular sieve (MCM-22) zeolite molecular sieve support type composite catalyst obtained have compared with
Good catalytic oxidation performance, and it is substantially better than pure molybdenum catalyst and pure titanium catalyst.Therefore, the present invention for oxidation sweetening and
Speech is supported between the molybdenum trioxide and titanium dioxide on zeolite molecular sieve and there is synergistic effect.Particularly when the matter of molybdenum and titanium
Synergy is best when amount is than being 1: 4, this makes zeolite molecular sieve support type composite catalyst (A1) reach best catalysis oxygen
Change effect.In addition, gas chromatographic detection sulfur content the result shows that: the total sulfur content of dibenzothiophenes and its product be 0, i.e., this
Total sulfur content < 10ppmw in invention gained oil product, meets five standard of Europe, total desulfurization degree is up to 100%.
Embodiment 7
That investigates zeolite molecular sieve support type composite catalyst of the present invention recycles performance, comprising the following steps:
(1) zeolite molecular sieve support type composite catalyst (A1) obtained in 0.10g embodiment 1 is taken, 20mL is added to, contains
Sulphur concentration is to be added in dibenzothiophenes-normal octane solution (the as simulation petroleum containing dibenzothiophenes) of 500ppmw
280 μ L, cyclohexanone peroxide (oxidant, O/S=2) solution that mass fraction is 50%, in the oil bath pan that temperature is 100 DEG C
30min is reacted under magnetic agitation.
(2) after the reaction was completed, reaction product solution is filtered, and flushed with n,N-dimethylacetamide and ethyl alcohol respectively
Obtained zeolite molecular sieve support type composite catalyst is filtered, drying is placed in Muffle furnace, is risen to the heating rate of 5 DEG C/min
550 DEG C of roasting 3h.The catalyst circulation obtained after roasting is handled into dibenzothiophenes-normal octane solution, other conditions and step
(1) identical, total circular treatment 8 times.
It being cooled to room temperature after the completion of each reaction, the content of sulphur in dibenzothiophenes in products therefrom solution is reacted in measurement,
And the conversion ratio of sulphur in dibenzothiophenes is obtained by calculating, as a result as shown in Figure 4.
Fig. 4 is zeolite molecular sieve support type composite catalyst in the embodiment of the present invention 7 to the circulation of sulphur in dibenzothiophenes
Treatment effect figure.As shown in Figure 4, the conversion ratio of sulphur is still without being decreased obviously, after operation 8 times for activity after catalyst continuous operation 5 times
Up to 93.16%, it is preferable to show that zeolite molecular sieve support type composite catalyst of the present invention has dibenzothiophenes oxidation sweetening
Power of regeneration is a kind of novel solid phase supported catalyst economical and practical, catalytic oxidation performance is good, to recycle performance good.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. the zeolite molecular sieve support type composite catalyst of dibenzothiophenes in a kind of removal oil product, which is characterized in that the boiling
The molecular sieve carried type composite catalyst of stone be using zeolite molecular sieve as carrier, on the zeolite molecular sieve load have molybdenum trioxide and
Titanium dioxide.
2. zeolite molecular sieve support type composite catalyst according to claim 1, which is characterized in that the zeolite molecular sieve
The mass ratio of molybdenum and titanium is 1~4: 4~1 in support type composite catalyst；In the zeolite molecular sieve support type composite catalyst
The gross mass of molybdenum and titanium is the 20%~25% of zeolite molecular sieve.
3. zeolite molecular sieve support type composite catalyst according to claim 2, which is characterized in that institute's zeolite molecular sieve is
MCM-22。
4. the zeolite molecular sieve support type of dibenzothiophenes in a kind of removal oil product according to any one of claims 1 to 3
The preparation method of composite catalyst, which comprises the following steps:
S1, zeolite molecular sieve is made to zeolite molecular sieve suspension；
S2, zeolite molecular sieve suspension, tetrabutyl titanate solution obtained in step S1 and Ammoniun Heptamolybdate Solution are mixed, is stirred
It mixes, impregnates, be centrifuged, drying obtains precursor mixture；
S3, precursor mixture obtained in step S2 is roasted, obtains zeolite molecular sieve support type composite catalyst.
5. the preparation method according to claim 4, which is characterized in that in the step S2, by tetrabutyl titanate solution and
Ammoniun Heptamolybdate Solution is added drop-wise in zeolite molecular sieve suspension simultaneously；The drop rate of the tetrabutyl titanate solution is 1.5mL/
Min~2.5mL/min；The drop rate of the Ammoniun Heptamolybdate Solution is 1.5mL/min~2.5mL/min.
6. preparation method according to claim 5, which is characterized in that in the step S2, the revolving speed of the stirring is
1000r/min~2000r/min；The time of the stirring is 2h~4h；The time of the dipping is 20h~30h；The centrifugation
Revolving speed be 5000r/min~6000r/min.
7. the preparation method according to any one of claim 4~6, which is characterized in that in the step S1, the zeolite
The preparation method of molecular sieve suspension the following steps are included:
(1) zeolite molecular sieve is mixed with ammonium nitrate solution, is stirred, cleaned, drying repeats aforesaid operations 2~3 times；
(2) zeolite molecular sieve after drying in step (1) is roasted；
(3) zeolite molecular sieve after roasting in step (2) is mixed with water, ultrasound, stirring obtains zeolite molecular sieve suspension.
8. preparation method according to claim 7, which is characterized in that in the step (1), the zeolite molecular sieve and nitre
The ratio of acid ammonium solution is 0.5g: 50mL；The concentration of the ammonium nitrate solution is 1mol/L；The stirring is in the case where temperature is 80 DEG C
It carries out；The time of the stirring is 2h；The drying carries out under vacuum conditions；The temperature of the drying is 80 DEG C；
In the step (2), the heating rate in the roasting process is 5 DEG C/min；It is described roasting temperature be 550 DEG C at into
Row；The time of the roasting is 3h；
In the step (3), the ratio of zeolite molecular sieve and water after the roasting is 0.5g: 50mL；The time of the ultrasound
For 30min.
9. the preparation method according to any one of claim 4~6, which is characterized in that in the step S3, the roasting
Heating rate is 5 DEG C/min in the process；The roasting carries out at being 550 DEG C in temperature；The time of the roasting is 3h.
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