CN110152722A - A method of synthesis zeolite support type composite catalyst is assisted using polyvinylpyrrolidone - Google Patents
A method of synthesis zeolite support type composite catalyst is assisted using polyvinylpyrrolidone Download PDFInfo
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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
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a kind of methods for assisting synthesis zeolite support type composite catalyst using polyvinylpyrrolidone, method includes the following steps: preparing zeolite molecular sieve suspension；Zeolite molecular sieve suspension and polyvinylpyrrolidone are mixed and made into zeolite molecular sieve mixed liquor；Zeolite molecular sieve mixed liquor, tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution are mixed and made into precursor mixture；Precursor mixture roast, composite catalyst of the present invention is made.Preparation method of the present invention has many advantages, such as that simple process, easy to operate, raw material are cheap and easy to get, preparation cost is cheap, short preparation period; the batch preparation of scale can be achieved; conducive to industrialized utilization; its composite catalyst obtained has many advantages, such as that economical and practical, stability is good, catalytic oxidation performance is good, it is good to recycle performance; can ultra high efficiency and ultra-deep oxidation sweetening, have fabulous economic benefit and application prospect.
Description
Technical field
The invention belongs to heterogeneous catalysis technology and its technical field of petrochemical industry, it is related to a kind of utilizing polyvinylpyrrolidone
The method for assisting synthesis zeolite support type composite catalyst.
Background technique
In recent years, it is got worse by the atmosphere polluting problem that sulfur-containing organic compound in fuel generates.These organic sulfides
It closes object to react in automobile engine combustion process with oxygen, directly results in SOx discharge, this is the master of air pollution and acid rain
Want one of source.In addition, sulfur-containing organic compound has corrosiveness to internal combustion engine of motor vehicle component in fuel.In order to cope with these
Challenge, many countries have formulated the new spec of fuel sulfur content.For example, the sulphur concentration in oil and gasoline limits respectively in the U.S.
System is in 15ppmw and 30ppmw or less.Therefore, depth and desulfurization rapidly are extremely urgent at present study a question.
For other sulfur methods, the organic sulfur compound that oxidation sweetening method removes in petroleum is considered as most having
The sulfur method of prospect.Oxidation sweetening method have operating condition it is mild, it is easy to operate, to sulfur heterocyclic compound such as dibenzo thiophene
The advantages that pheno (DBT) and its derivative efficient removal, in the presence of suitable catalysts, oxidant, can be by organic sulfurs difficult to degrade
Compound is converted into sulfoxide or sulfone, these products are then removed by polar extraction, to obtain the fuel of super-low sulfur.Therefore, high
Imitating quick catalyst is always the hot spot that researchers inquire into.In recent years, all searchings of many researchers prepare a kind of property
The excellent oxidation-desulfurizing catalyst of energy.Catalyst in relation to organic sulfur compound in catalysis oxidation petroleum there are many report.Such as:
The solid phase supported catalysts such as metal oxide, metal organic framework (MOF) supported catalyst are widely used in catalysis oxidation petroleum
Desulfurization.However, there are preparation process in the preparation method of existing most of solid phase supported catalysts comparatively laborious, manufacturing cycle
Long, the problems such as preparation cost is relatively high, and many transition metal are not easy successfully to be supported on carrier, it is negative that this severely limits solid phases
The practical application of supported catalyst.In addition, selection exists in existing synthetic method in order to which transition metal to be successfully supported on carrier
Hydro-thermal reaction synthetic catalyst is carried out under conditions of high temperature and pressure, but these synthetic method existence conditions are harsh, at high cost etc.
Disadvantage.In addition, existing solid phase supported catalyst is used to still have higher cost, catalysis oxidation when catalysis oxidation petroleum sweetening
The problems such as performance is insufficient, regenerability is poor, which also limits the extensive uses of solid phase supported catalyst.
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 simple process, operation side
Just, raw material are cheap and easy to get, preparation cost is cheap, the utilization polyvinylpyrrolidone of short preparation period assists synthetic zeolite molecule
The method for sieving support type composite catalyst, thus obtained zeolite molecular sieve support type composite catalyst have that stability is good, urges
Change oxidation susceptibility is good, recycles the advantages that performance is good.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A method of using polyvinylpyrrolidone assistance synthesis zeolite support type composite catalyst, including with
Lower step:
S1, zeolite molecular sieve is made to zeolite molecular sieve suspension；
S2, zeolite molecular sieve suspension obtained in step S1 is mixed with polyvinylpyrrolidone, stirs, obtains zeolite
Molecular sieve mixed liquor；
S3, zeolite molecular sieve mixed liquor, tetrabutyl titanate solution obtained in step S2 and Ammoniun Heptamolybdate Solution are mixed,
Stirring is centrifuged, and drying obtains precursor mixture；
S4, precursor mixture obtained in step S3 is roasted, obtains zeolite molecular sieve support type composite catalyzing
Agent.
Above-mentioned method, further improved, the zeolite molecules in the step S2, in the zeolite molecular sieve suspension
The mass ratio of sieve and polyvinylpyrrolidone is 5: 3~5: 5.
Above-mentioned 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 30min~60min.
Above-mentioned method, it is further improved, it is in the step S3, tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution is same
When be added drop-wise in zeolite molecular sieve mixed liquor；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.
Above-mentioned method, it is further improved, in the step S3, the revolving speed of the stirring be 1000r/min~
2000r/min；The time of the stirring is 2h~4h；The revolving speed of the centrifugation is 5000r/min~6000r/min.
Above-mentioned method, it is further improved, in the step S1, the preparation method packet of the zeolite molecular sieve suspension
Include following steps:
(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 method, it is further improved, in the step (1), the ratio of the zeolite molecular sieve and ammonium nitrate solution
Example is 0.5g: 50mL；The concentration of the ammonium nitrate solution is 1mol/L；The stirring carries out at being 80 DEG C in temperature；It is described to stir
The time mixed 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 method, further improved, in the step S4, heating rate is 5 DEG C/min in the roasting process；
The roasting carries out at being 550 DEG C in temperature；The time of the roasting is 3h.
Above-mentioned method, it is further improved, zeolite molecular sieve support type composite catalyst made from the method be with
Zeolite molecular sieve is carrier, and load has molybdenum trioxide and titanium dioxide on the zeolite molecular sieve.
Above-mentioned method, further improved, the quality of molybdenum and titanium in the zeolite molecular sieve support type composite catalyst
Than being 1~4: 4~1；The gross mass of molybdenum and titanium is zeolite molecular sieve in the zeolite molecular sieve support type composite catalyst
20%~25%；Institute's zeolite molecular sieve is MCM-22.
Compared with the prior art, the advantages of the present invention are as follows:
(1) synthesis zeolite support type composite catalyzing is assisted using polyvinylpyrrolidone the present invention provides a kind of
The method of agent, using zeolite molecular sieve, tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution as raw material, by being added during the preparation process
Polyvinylpyrrolidone assists synthesis zeolite support type composite catalyst.In the present invention, polyvinylpyrrolidone used
As high molecular surfactant, play the role of adhesive, molybdenum and titanium can be more efficiently supported on MCM-22 carrier
On, to greatly shorten the preparation time of catalyst.Preparation method of the present invention has simple process, easy to operate, raw material
Cheap and easy to get, the advantages that preparation cost is cheap, short preparation period, it can be achieved that prepared by the batch of scale, is conducive to industrialized utilization.
(2) zeolite molecular sieve support type composite catalyst obtained in the present invention, using zeolite molecular sieve as carrier, zeolite point
Load has molybdenum trioxide and titanium dioxide on son sieve.In the present invention, zeolite molecular sieve is good, rich with its large specific surface area, stability
The advantages that acidic site of richness is a kind of most suitable carrier.In addition, since molybdenum trioxide and titanium dioxide have price low
Honest and clean, nontoxic, the advantages that thermal stability is high, chemical stability is high, thus by molybdenum trioxide and titanium dichloride load in zeolite
On molecular sieve, so that the advantages of composite catalyst set the two, have that low in cost, nontoxic, thermal stability is high, chemical
The advantages that stability is high.In addition, showing composite catalyst on zeolite molecular sieve molybdenum trioxide and titanium dichloride load
Preferable regenerability out, and under the action of polyvinylpyrrolidone by molybdenum trioxide and titanium dichloride load in zeolite molecules
On sieve but also the structure of composite catalyst is more stable, performance is recycled to be conducive to improve composite catalyst.This
Invention zeolite molecular sieve support type composite catalyst is with economical and practical, stability is good, catalytic oxidation performance is good, recycling property
Can be good the advantages that, when the sulfur-bearing organic pollutant being used in removal oil product can realization quickly and efficiently to sulfur-bearing
Effective conversion of organic pollutant, reaches ultra high efficiency and ultra-deep oxidation sweetening, before having fabulous economic benefit and application
Scape.
(3) in the present invention in zeolite molecular sieve support type composite catalyst obtained the mass ratio of molybdenum and titanium be 1~4: 4~
1, and the gross mass of molybdenum and titanium is the 20%~25% of zeolite molecular sieve, wherein the mass ratio of molybdenum and titanium refers to for 1~4: 4~1
A ratio between molybdenum and the two activated centres of titanium, and the gross mass of molybdenum and titanium is for the 20%~25% of zeolite molecular sieve
Refer to that activated centre accounts for a ratio of carrier, by optimizing the mass ratio and molybdenum titanium gross mass accounting of molybdenum and titanium, further mentions
The catalytic oxidation performance and regenerability for rising catalyst are realized more inexpensive, more to obtain better catalytic oxidation effect
Efficient catalysis oxidation can convert to high efficiency, low cost the sulfur-bearing organic pollutant in petroleum.
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 synthesis technology flow diagram of zeolite molecular sieve support type composite catalyst in the embodiment of the present invention 1.
Fig. 2 schemes for the SEM of zeolite molecular sieve support type composite catalyst obtained in the embodiment of the present invention 1.
Fig. 3 is for different catalysts in the embodiment of the present invention 6 to sulphur in dibenzothiophenes under differential responses time conditions
Changing 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
A method of synthesis zeolite support type composite catalyst, synthesis are assisted using polyvinylpyrrolidone
Process 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) MCM-22 mixed liquor is prepared:
Mass ratio according to zeolite molecular sieve and polyvinylpyrrolidone in zeolite molecular sieve suspension is 5: 4, will be gathered
Vinylpyrrolidone is added in MCM-22 suspension obtained in step (1), to stir under the mixing speed of 1500r/min
30min obtains MCM-22 mixed liquor.
(3) precursor mixture is prepared:
(3.1) 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.
(3.2) under the conditions of stirring (revolving speed 1500r/min) by tetrabutyl titanate solution obtained in step (3.1) and
Ammoniun Heptamolybdate Solution is added drop-wise to simultaneously in step (2) in MCM-22 mixed liquor 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,
It is 5000r/min centrifugation in revolving speed, drying obtains precursor mixture.In the present invention by optimization tetrabutyl titanate solution and
The drop rate of Ammoniun Heptamolybdate Solution enables to tetrabutyl titanate and ammonium heptamolybdate to be evenly distributed on MCM-22 carrier, and
Molybdenum trioxide is prepared by subsequent calcination process and titanium dioxide is evenly distributed on composite catalyst on MCM-22 carrier,
This is because drop rate will lead to the hydrolysis of tetrabutyl titanate solution slowly excessively, and too fast it will lead to tetrabutyl titanate solution and seven molybdenums
Acid ammonium solution uneven distribution is eventually collected on MCM-22 carrier, so as to cause three oxygen generated during subsequent calcination process
Change molybdenum and titanium dioxide is difficult to be evenly distributed on MCM-22 carrier.
(4) zeolite molecular sieve support type composite catalyst is prepared:
It is 5 DEG C/min according to heating rate, precursor mixture obtained in step (3) is warming up to 550 DEG C of roasting 3h,
Obtain zeolite molecular sieve support type composite catalyst, as MoO3-TiO2/ MCM-22, number MT-1: 4.In the present invention, pass through
On the one hand roasting is to remove extra moisture and unstable material, i.e., under the high temperature conditions transform into titanium source and molybdenum source respectively
The titanium dioxide and molybdenum trioxide product of catalytic action are played, the structure of catalyst is on the other hand promoted by calcining at high temperature
Stability keeps catalyst more stable under subsequent progress oxidation sweetening experimental condition.
Zeolite molecular sieve support type composite catalyst obtained in the present embodiment, using zeolite molecular sieve as carrier, zeolite point
Load has molybdenum trioxide and titanium dioxide on son sieve, wherein the quality of molybdenum and titanium in zeolite molecular sieve support type composite catalyst
Than being 1: 4, and the gross mass of molybdenum and titanium is the 23.19% of zeolite molecular sieve.
Fig. 2 schemes for the SEM of zeolite molecular sieve support type composite catalyst obtained in the embodiment of the present invention 1.It can by Fig. 2
Know, MCM-22 carrier is sheet, and titanium dioxide is large particulate matter, and molybdenum trioxide is little particle, and molybdenum trioxide particles and
Titanium dioxide granule is supported on the MCM-22 carrier of sheet.
Embodiment 2
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 MT-2: 3 in embodiment 2.
Zeolite molecular sieve support type composite catalyst (MT-2: 3) obtained in the present embodiment, the zeolite point with embodiment 1
Son sieve support type composite catalyst (MT-1: 4) is essentially identical, and difference is only that: the zeolite molecular sieve support type of embodiment 2 is compound
The mass ratio of molybdenum and titanium is 2: 3 in catalyst.
Embodiment 3
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 MT-1: 1 in embodiment 3.
Zeolite molecular sieve support type composite catalyst (MT-1: 1) obtained in the present embodiment, the zeolite point with embodiment 1
Son sieve support type composite catalyst (MT-1: 4) is essentially identical, and difference is only that: the zeolite molecular sieve support type of embodiment 3 is compound
The mass ratio of molybdenum and titanium is 1: 1 in catalyst.
Embodiment 4
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 MT-3: 2 in embodiment 4.
Zeolite molecular sieve support type composite catalyst (MT-3: 2) obtained in the present embodiment, the zeolite point with embodiment 1
Son sieve support type composite catalyst (MT-1: 4) is essentially identical, and difference is only that: the zeolite molecular sieve support type of embodiment 4 is compound
The mass ratio of molybdenum and titanium is 3: 2 in catalyst.
Embodiment 5
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 MT-4: 1 in embodiment 5.
Zeolite molecular sieve support type composite catalyst (MT-4: 1) obtained in the present embodiment, the zeolite point with embodiment 1
Son sieve support type composite catalyst (MT-1: 4) is essentially identical, and difference is only that: the zeolite molecular sieve support type of embodiment 5 is compound
The mass ratio of molybdenum and titanium is 4: 1 in catalyst.
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 MT-0: 5.
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 MT-5: 0.
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 obtained in Example 1-5 (MT-1: 4, MT-2: 3, MT-1: 1,
MT-3: 2, MT-4: 1), titanium dioxide/zeolite molecular sieve composite catalyst (MT-0: 5) obtained in comparative example 1, in comparative example 2
Molybdenum trioxide obtained/zeolite molecular sieve composite catalyst (MT-5: 0), each 0.10g are added separately to 20mL, are containing sulphur concentration
In dibenzothiophenes (DBT)-normal octane solution (the as simulation petroleum containing dibenzothiophenes) of 500ppmw, it is separately added into
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, completes the removal to 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 for different catalysts in the embodiment of the present invention 6 to sulphur in dibenzothiophenes under differential responses time conditions
Changing effect figure.From the figure 3, it may be seen that zeolite molecular sieve support type composite catalyst (MT-1: 4, MT-2: 3, MT- produced by the present invention
1: 1, MT-3: 2, MT-4: 1) dibenzothiophenes in oil product can be effectively converted, wherein zeolite molecular sieve support type is compound
Conversion of the catalyst (MT-1: 4, MT-2: 3, MT-1: 1, MT-3: 2, MT-4: 1) when reacting 10min to sulphur in dibenzothiophenes
Rate is respectively 98.14%, 81.54%, 75.46%, 73.38%, 69.95%, when reacting 30min to sulphur in dibenzothiophenes
Conversion ratio be respectively 100%, 100%, 99.73%, 99.2%, 98.18%, and titanium dioxide/boiling obtained in comparative example 1
Stone molecular sieve composite catalyst (MT-0: 5) is respectively to the conversion ratio of sulphur in dibenzothiophenes when reacting 10min, 30min
45.51% and 67.43%, molybdenum trioxide/zeolite molecular sieve composite catalyst (MT-5: 0) obtained is reacting in comparative example 2
It is respectively 23.9% and 54.31% to the conversion ratio of sulphur in dibenzothiophenes when 10min, 30min.The above result shows that this hair
Zeolite molecular sieve support type that is bright while being obtained molybdenum trioxide and titanium dichloride load on zeolite molecular sieve (MCM-22) is multiple
Closing catalyst has preferable catalytic oxidation performance, and is substantially better than pure molybdenum catalyst and pure titanium catalyst.Therefore, the present invention couple
For oxidation sweetening, it is supported between the molybdenum trioxide and titanium dioxide on zeolite molecular sieve and there is synergistic effect.Particularly
When the mass ratio of molybdenum and titanium is 1: 4, synergy is best, this makes zeolite molecular sieve support type composite catalyst (MT-1: 4)
Reach best catalytic oxidation effect.In addition, gas chromatographic detection sulfur content the result shows that: dibenzothiophenes and its product
Total sulfur content is 0, i.e. total sulfur content < 10ppmw in present invention gained oil product, meets five standard of Europe, total desulfurization degree is up to
100%.
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 (10)
1. a kind of method for assisting synthesis zeolite support type composite catalyst using polyvinylpyrrolidone, feature exist
In, comprising the following steps:
S1, zeolite molecular sieve is made to zeolite molecular sieve suspension；
S2, zeolite molecular sieve suspension obtained in step S1 is mixed with polyvinylpyrrolidone, stirs, obtains zeolite molecules
Sieve mixed liquor；
S3, zeolite molecular sieve mixed liquor, tetrabutyl titanate solution obtained in step S2 and Ammoniun Heptamolybdate Solution are mixed, is stirred
It mixes, is centrifuged, drying obtains precursor mixture；
S4, precursor mixture obtained in step S3 is roasted, obtains zeolite molecular sieve support type composite catalyst.
2. the method according to claim 1, wherein in the step S2, in the zeolite molecular sieve suspension
Zeolite molecular sieve and polyvinylpyrrolidone mass ratio be 5: 3~5: 5.
3. according to the method described in claim 2, it is characterized in that, the revolving speed of the stirring is 1000r/ in the step S2
Min~2000r/min；The time of the stirring is 30min~60min.
4. method described in any one of claim 1 to 3, which is characterized in that in the step S3, by tetrabutyl titanate
Solution and Ammoniun Heptamolybdate Solution are added drop-wise in zeolite molecular sieve mixed liquor 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.
5. according to the method described in claim 4, it is characterized in that, the revolving speed of the stirring is 1000r/ in the step S3
Min~2000r/min；The time of the stirring is 2h~4h；The revolving speed of the centrifugation is 5000r/min~6000r/min.
6. method described in any one of claim 1 to 3, which is characterized in that in the step S1, the zeolite molecules
Sieve suspension preparation 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 with water, ultrasound, stirring obtains zeolite molecular sieve suspension.
7. according to the method described in claim 6, it is characterized in that, in the step (1), the zeolite molecular sieve and ammonium nitrate
The ratio of solution is 0.5g: 50mL；The concentration of the ammonium nitrate solution is 1mol/L；It is described stirring temperature be 80 DEG C at into
Row；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.
8. method described in any one of claim 1 to 3, which is characterized in that in the step S4, the roasting process
Middle heating rate is 5 DEG C/min；The roasting carries out at being 550 DEG C in temperature；The time of the roasting is 3h.
9. method described in any one of claim 1 to 3, which is characterized in that zeolite molecular sieve made from the method
Support type composite catalyst is using zeolite molecular sieve as carrier, and load has molybdenum trioxide and titanium dioxide on the zeolite molecular sieve
Titanium.
10. according to the method described in claim 9, it is characterized in that, molybdenum in the zeolite molecular sieve support type composite catalyst
Mass ratio with titanium is 1~4: 4~1；The gross mass of molybdenum and titanium is zeolite in the zeolite molecular sieve support type composite catalyst
The 20%~25% of molecular sieve；Institute's zeolite molecular sieve is MCM-22.
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