CN105664998A - Preparation method for Ti/MCM-41 molecular sieve having catalytically oxidizing activity and application thereof - Google Patents
Preparation method for Ti/MCM-41 molecular sieve having catalytically oxidizing activity and application thereof Download PDFInfo
- Publication number
- CN105664998A CN105664998A CN201511008942.5A CN201511008942A CN105664998A CN 105664998 A CN105664998 A CN 105664998A CN 201511008942 A CN201511008942 A CN 201511008942A CN 105664998 A CN105664998 A CN 105664998A
- Authority
- CN
- China
- Prior art keywords
- mcm
- molecular sieve
- catalytic oxidation
- preparation
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
-
- 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
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A preparation method for a Ti/MCM-41 molecular sieve having a catalytically oxidizing activity and an application thereof. In the invention, a preparation method for the Ti/MCM-41 molecular sieve and an application thereof are designed for solving the problem of low catalytically oxidizing desulfurization efficiency of a Ti/MCM-41 molecular sieve in the prior art. The method includes the steps of: 1) pre-treating MCM-41 molecular sieve in a muffle furnace; 2) uniformly dispersing an organic titanium source in ethanol, adding the MCM-41 molecular sieve, performing ultrasonic treatment and aging the molecular sieve at room temperature, and then stirring the molecular sieve in an oil bath until water and ethanol volatilize completely, and finally drying the molecular sieve to obtain a white solid; and 3) calcining the white solid in a muffle furnace to obtain the Ti/MCM-41 molecular sieve. The Ti/MCM-41 molecular sieve has excellent effect on a catalytically oxidizing desulfurization reaction at room temperature, and is more than 97% in conversion rate on dibenzothiophene in a reaction at the room temperature for 10 min.
Description
Technical field
The present invention designs preparation method and the application thereof of a kind of Ti/MCM-41 molecular sieve.
Background technology
From Mobil company of the U.S. since reported first mesoporous material M41S Series Molecules sieve in 1992, the research of MCM-41 is reported constantly occur both at home and abroad. MCM-41 molecular sieve is the solid acid catalysis new material of a class extensive application prospect, has an one-dimensional linear duct of hexagonal prism structure, good hydrothermal stability, its aperture can between 2～8nm modulation, and specific surface area is more than 700m2/ g, namely this molecular sieve has the features such as aperture narrowly distributing, specific surface area and adsorption capacity are big to be widely used in heterogeneous catalysis, adsorbs and the field such as separate. But, owing to the lattice defect in MCM-41 framework of molecular sieve is less, cause its catalysis activity not high, particularly in many catalytic selective oxidations react, its application is very restricted. MCM-41 skeleton introduces the metal heteroatom with redox characteristic, its lattice defect can be increased, improve the activity of catalyst, thus preparing the novel catalyst with unique catalytic function, transition metal as titanium, vanadium, chromium, zirconium, manganese, molybdenum, tungsten etc. have redox ability embeds framework of molecular sieve, can catalytic selective oxidation larger molecular organics. At present, the titanium-silicone metapore material such as Ti/MCM-41, Ti/HMS, Ti/MCM-48 it has been reported that wherein most study or Ti/MCM-41. 1994, Ti metal ion was introduced MCM-41 molecular sieve by Corma.A et al., is prepared for Ti/MCM-41 molecular sieve. Owing to Ti metal ion has the feature such as interchangeability and valence state transmutability, after being introduced into framework of molecular sieve, the lattice defect quantity in MCM-41 molecular sieve can be increased, and improve the redox ability of molecular sieve, thus significantly improving its catalytic performance, especially to the chemical reaction participated in containing macromolecular organic compound, show the catalytic performance of excellence, therefore, Ti/MCM-41 molecular sieve has tremendous expansion potentiality at catalytic field.
Desulfurization has significant effect for improving oil quality, minimizing discharge of poisonous waste, improving the aspects such as fuel oil efficiency of combustion. Sulfur method mainly has hydrodesulfurization, oxidation sweetening, adsorbs desulfurization, abstraction desulfurization etc. But the pressure and temperature of equipment is had high requirements by hydrodesulfurization when deep desulfuration, cost is too high; The adsorbent of absorption desulfurization is generally the molecular sieve that noble metal supports and deep desulfuration poor effect; Abstraction desulfurization is from a phase transfer to another phase by sulfur containing species, and substantially sulfur containing species changes; And oxidation sweetening is not only low for equipment requirements but also can carry out deep desulfuration, therefore more research work is around what oxidation sweetening carried out at present.
Existing document and document announcement Ti/MCM-41 molecular sieve is for oxidation sweetening, but the preparation of Ti/MCM-41 molecular sieve is complicated, and catalytic oxidation desulfurization is inefficient.
Summary of the invention
The present invention is to solve the Ti/MCM-41 inefficient problem of molecular sieve catalytic oxidation sweetening prepared by existing method, and provides preparation method and the application thereof of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity.
The preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity of the present invention sequentially includes the following steps:
One, MCM-41 molecular sieve is placed in Muffle furnace, is calcining 3h～5h under 450 DEG C～600 DEG C conditions in temperature, obtains pretreated MCM-41 molecular sieve;
Two, organic titanium source is dispersed in ethanol, it is subsequently adding the pretreated MCM-41 molecular sieve that step one obtains, stirring 5min～10min, then at supersonic frequency be 28kHz-40kHz when supersound process 10min～30min, then deionized water it is added dropwise over, at room temperature stir 1.5h～2.5h, then ageing 10h～14h, place into the oil bath that temperature is 35～45 DEG C to be stirred to water and ethanol and volatilize completely, then dry 3h～5h when temperature is 90～110 DEG C, obtains white solid; The ratio of the quality in described organic titanium source and the volume of ethanol is 1.53g:(10～50) mL; The mass ratio of the pretreated MCM-41 molecular sieve that described organic titanium source and step one obtain is (5～30): 100; The volume ratio of described deionized water and ethanol is (0.09～0.018): 1;
Three, the white solid obtained in step 2 is placed in Muffle furnace, is 150～600 DEG C of calcining 3h～5h in temperature, obtains Ti/MCM-41 molecular sieve.
A kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity of the present invention is applied to the oxidation sweetening reaction of the simulated oil system being sulfur containing species with dibenzothiophenes as catalyst.
The method have the benefit that
1, the catalyst that the Ti/MCM-41 molecular sieve of the present invention reacts as catalytic oxidation desulfurization, it is less costly, and preparation technology is relatively simple, and reaction condition is gentle, can be applicable to large-scale production.
2, the Ti/MCM-41 molecular sieve of the present invention at room temperature catalytic oxidation desulfurization reaction effect is excellent, and the conversion ratio at room temperature reacting ten minutes dibenzothiophenes reaches more than 97%, namely at room temperature can reach the effect of desulfurization rapidly.
Accompanying drawing explanation
Fig. 1 is checking test (one) N2Adsorption and desorption isotherms comparison diagram; Wherein a is MCM-41 molecular sieve N under 77K2Adsorption and desorption isotherms; B is the N testing a Ti/MCM-41 molecular sieve prepared under 77K2Adsorption and desorption isotherms; C is the N testing the two Ti/MCM-41 molecular sieves prepared under 77K2Adsorption and desorption isotherms; D is the N testing the three Ti/MCM-41 molecular sieves prepared under 77K2Adsorption and desorption isotherms; E is the N testing the four Ti/MCM-41 molecular sieves prepared under 77K2Adsorption and desorption isotherms; F is that tetrabutyl titanate hydrolysis obtains the hydroxide of titanium N under 77K2Adsorption and desorption isotherms;
Fig. 2 is desulfurization curve comparison figure; Wherein 1 is the desulfurization curve of the hydroxide of titanium, and 2 is the desulfurization curve of Ti/MCM-41 molecular sieve that b is that test one prepares; The desulfurization curve of the 3 Ti/MCM-41 molecular sieves prepared for test two; The desulfurization curve of the 4 Ti/MCM-41 molecular sieves prepared for test three; The desulfurization curve of the 5 Ti/MCM-41 molecular sieves prepared for test four.
Detailed description of the invention
Detailed description of the invention one: the preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity of present embodiment sequentially includes the following steps:
One, MCM-41 molecular sieve is placed in Muffle furnace, is calcining 3h～5h under 450 DEG C～600 DEG C conditions in temperature, obtains pretreated MCM-41 molecular sieve;
Two, organic titanium source is dispersed in ethanol, it is subsequently adding the pretreated MCM-41 molecular sieve that step one obtains, stirring 5min～10min, then at supersonic frequency be 28kHz～40kHz when supersound process 10min～30min, then deionized water it is added dropwise over, at room temperature stir 1.5h～2.5h, then ageing 10h～14h, place into the oil bath that temperature is 35～45 DEG C to be stirred to water and ethanol and volatilize completely, then dry 3h～5h when temperature is 90～110 DEG C, obtains white solid; The ratio of the quality in described organic titanium source and the volume of ethanol is 1.53g:(10～50) mL; The mass ratio of the pretreated MCM-41 molecular sieve that described organic titanium source and step one obtain is (5～30): 100; The volume ratio of described deionized water and ethanol is (0.018～0.09): 1;
Three, the white solid obtained in step 2 is placed in Muffle furnace, is 150～600 DEG C of calcining 3h～5h in temperature, obtains Ti/MCM-41 molecular sieve.
In step 3 when temperature controls in 150 DEG C～350 DEG C intervals, the product obtained is light yellow solid powder; When temperature controls in 350 DEG C～600 DEG C intervals, the product obtained is white solid powder.
The catalyst that the Ti/MCM-41 molecular sieve of present embodiment reacts as catalytic oxidation desulfurization, it is less costly, and preparation technology is relatively simple, and reaction condition is gentle, can be applicable to large-scale production.
The Ti/MCM-41 molecular sieve of present embodiment at room temperature catalytic oxidation desulfurization reaction effect is excellent, and the conversion ratio at room temperature reacting ten minutes dibenzothiophenes reaches more than 97%, namely at room temperature can reach the effect of desulfurization rapidly.
Detailed description of the invention two: present embodiment and detailed description of the invention one the difference is that: step one is calcining 4h under 500 DEG C～550 DEG C conditions in temperature, obtains pretreated MCM-41 molecular sieve. Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two the difference is that: the organic titanium source described in step 2 is butyl titanate, tetraethyl titanate or isopropyl titanate. Other step and parameter are identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three are 1.53g:(20～40 the difference is that the ratio of: the quality in the organic titanium source described in step 2 with the volume of ethanol) mL. Other step is identical with one of detailed description of the invention one to three with parameter.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four are 1.53g:30mL the difference is that the ratio of: the quality in the organic titanium source described in step 2 with the volume of ethanol. Other step is identical with one of detailed description of the invention one to four with parameter.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five the difference is that: the mass ratio of the pretreated MCM-41 molecular sieve that the organic titanium source described in step 2 and step one obtain is (10～20): 100 other steps are identical with one of detailed description of the invention one to five with parameter.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six the difference is that: in step 2 in supersonic frequency is 30kHz when supersound process 20min. Other step is identical with one of detailed description of the invention one to six with parameter.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven the difference is that: step 2 at room temperature stirs 2h, then ageing 12h, places into the oil bath that temperature is 40 DEG C to be stirred to water and ethanol and volatilize completely.Other step is identical with one of detailed description of the invention one to seven with parameter.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight the difference is that: in step 2 when temperature is 100 DEG C dry 4h. Other step is identical with one of detailed description of the invention one to eight with parameter.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine the difference is that: step 3 is 350 DEG C of calcining 4h in temperature, obtains Ti/MCM-41 molecular sieve. Other step is identical with one of detailed description of the invention one to nine with parameter.
Detailed description of the invention 11: the oxidation sweetening reaction of the simulated oil system that it is sulfur containing species with dibenzothiophenes that a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity of present embodiment is applied to.
Detailed description of the invention 12: present embodiment and detailed description of the invention 11 the difference is that: the described simulated oil in simulated oil system is normal octane. Other steps and parameter and detailed description of the invention 11 are identical.
By following verification experimental verification beneficial effects of the present invention:
Test one, a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity of this test preparation method sequentially include the following steps:
One, the MCM-41 molecular sieve of 3.798g is placed in Muffle furnace, is calcining 4h under 500 DEG C of conditions in temperature, obtains pretreated MCM-41 molecular sieve;
Two, 1.53g organic titanium source is dispersed in the ethanol of 10mL, it is subsequently adding the pretreated MCM-41 molecular sieve that step one obtains, stirring 5min, then at supersonic frequency be 30kHz when supersound process 20min, be then added dropwise over the deionized water of 0.9mL, at room temperature stir 2h, then ageing 12h, placing into stir in the oil bath that temperature is 40 DEG C and volatilize completely to water and ethanol, then the dry 4h when temperature is 100 DEG C, obtains white solid;
Three, the white solid obtained in step 2 is placed in Muffle furnace, is 150 DEG C of calcining 3h in temperature, obtains Ti/MCM-41 molecular sieve.
Test two, a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity of this test preparation method sequentially include the following steps:
One, the MCM-41 molecular sieve of 1.638g is placed in Muffle furnace, is calcining 4h under 500 DEG C of conditions in temperature, obtains pretreated MCM-41 molecular sieve;
Two, the organic titanium source of 1.53g is dispersed in the ethanol of 10mL, it is subsequently adding the pretreated MCM-41 molecular sieve that step one obtains, stirring 5min, then at supersonic frequency be 30kHz when supersound process 20min, be then added dropwise over the deionized water of 0.9mL, at room temperature stir 2h, then ageing 12h, placing into stir in the oil bath that temperature is 40 DEG C and volatilize completely to water and ethanol, then the dry 4h when temperature is 100 DEG C, obtains white solid;
Three, the white solid obtained in step 2 is placed in Muffle furnace, is 150 DEG C of calcining 3h in temperature, obtains Ti/MCM-41 molecular sieve.
Test three, a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity of this test preparation method sequentially include the following steps:
One, the MCM-41 molecular sieve of 0.55g is placed in Muffle furnace, is calcining 4h under 500 DEG C of conditions in temperature, obtains pretreated MCM-41 molecular sieve;
Two, the organic titanium source of 1.53g is dispersed in the ethanol of 10mL, it is subsequently adding the pretreated MCM-41 molecular sieve that step one obtains, stirring 5min, then at supersonic frequency be 30kHz when supersound process 20min, be then added dropwise over the deionized water of 0.9mL, at room temperature stir 2h, then ageing 12h, placing into stir in the oil bath that temperature is 40 DEG C and volatilize completely to water and ethanol, then the dry 4h when temperature is 100 DEG C, obtains white solid;
Three, the white solid obtained in step 2 is placed in Muffle furnace, is 150 DEG C of calcining 3h in temperature, obtains Ti/MCM-41 molecular sieve.
Test four, a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity of this test preparation method sequentially include the following steps:
One, the MCM-41 molecular sieve of 0.198g is placed in Muffle furnace, is calcining 3h～5h under 500 DEG C of conditions in temperature, obtains pretreated MCM-41 molecular sieve;
Two, the organic titanium source of 1.53g is dispersed in the ethanol of 10mL, it is subsequently adding the pretreated MCM-41 molecular sieve that step one obtains, stirring 5min, then at supersonic frequency be 30kHz when supersound process 20min, be then added dropwise over the deionized water of 0.9mL, at room temperature stir 2h, then ageing 12h, placing into stir in the oil bath that temperature is 40 DEG C and volatilize completely to water and ethanol, then the dry 4h when temperature is 100 DEG C, obtains white solid;
Three, the white solid obtained in step 2 is placed in Muffle furnace, is 150 DEG C of calcining 3h in temperature, obtains Ti/MCM-41 molecular sieve.
(1) Ti/MCM-41 molecular sieve is applied to catalytic oxidation desulfurization reaction, and concrete operations are as follows:
It is 1000ppm that sulfur containing species dibenzothiophenes is dissolved completely in simulated oil to sulfur content in simulated oil, when reaction temperature is room temperature (25 DEG C), it is separately added into MCM-41 molecular sieve, tetrabutyl titanate hydrolysis obtains the hydroxide of titanium, the Ti/MCM-41 molecular sieve that test one prepares, the Ti/MCM-41 molecular sieve that test two prepares, the Ti/MCM-41 molecular sieves that the Ti/MCM-41 molecular sieve that test three prepares and test four prepare are as catalyst, it is subsequently adding isopropyl benzene hydroperoxide as oxidant, wherein MCM-41 molecular sieve concentration in the simulated oil containing dibenzothiophenes is 5g/L, it is 5g/L that tetrabutyl titanate hydrolysis obtains the hydroxide of titanium concentration in the simulated oil containing dibenzothiophenes, the Ti/MCM-41 molecular sieve that test one prepares concentration in the simulated oil containing dibenzothiophenes is 5g/L, the Ti/MCM-41 molecular sieve that test two prepares concentration in the simulated oil containing dibenzothiophenes is 5g/L, the Ti/MCM-41 molecular sieve that test three prepares concentration in the simulated oil containing dibenzothiophenes is 5g/L, the Ti/MCM-41 molecular sieve that test four prepares concentration in the simulated oil containing dibenzothiophenes is 5g/L, the adding proportion of isopropyl benzene hydroperoxide is the mol ratio of O/S is 1:(4～15), simulated oil is normal octane.
(1) N under 77K is obtained2Adsorption and desorption isotherms comparison diagram as it is shown in figure 1, in Fig. 1 a be MCM-41 molecular sieve N under 77K2Adsorption and desorption isotherms; B is the N testing a Ti/MCM-41 molecular sieve prepared under 77K2Adsorption and desorption isotherms; C is the N testing the two Ti/MCM-41 molecular sieves prepared under 77K2Adsorption and desorption isotherms; D is the N testing the three Ti/MCM-41 molecular sieves prepared under 77K2Adsorption and desorption isotherms; E is the N testing the four Ti/MCM-41 molecular sieves prepared under 77K2Adsorption and desorption isotherms; F is that tetrabutyl titanate hydrolysis obtains the hydroxide of titanium N under 77K2Adsorption and desorption isotherms.
As can be seen from Figure 1, MCM-41 still suffers from obvious hysteresis loop after carrying out titanium load, for IV type adsorption curve, illustrates that the MCM-41 structure after supported titanium does not change.
(2) sample once at reaction 0min, 5min, 10min, 20min, 40min, 60min respectively, carry out chromatography, obtain desulfurization curve comparison figure as shown in Figure 2, in Fig. 2,1 is the desulfurization curve of the hydroxide of titanium, and 2 is the desulfurization curve of Ti/MCM-41 molecular sieve that b is that test one prepares;The desulfurization curve of the 3 Ti/MCM-41 molecular sieves prepared for test two; The desulfurization curve of the 4 Ti/MCM-41 molecular sieves prepared for test three; The desulfurization curve of the 5 Ti/MCM-41 molecular sieves prepared for test four.
As can be seen from Figure 2, when reducing titanium load capacity, reactivity increases therewith; When load capacity is reduced to 5%, the conversion ratio of dibenzothiophenes when 10min close to 100%. When the hydroxide of titanium is as the catalyst of catalytic oxidation desulfurization, the poor effect of its catalytic oxidation desulfurization. And the preparation method in the present invention can prepare the Ti/MCM-41 molecular sieve that catalytic oxidation desulfurization has fine catalysis activity, it at room temperature can reach the effect of desulfurization rapidly.
Claims (10)
1. the preparation method of a Ti/MCM-41 molecular sieve with catalytic oxidation activity, it is characterised in that the method sequentially includes the following steps:
One, MCM-41 molecular sieve is placed in Muffle furnace, is calcining 3h～5h under 450 DEG C～600 DEG C conditions in temperature, obtains pretreated MCM-41 molecular sieve;
Two, organic titanium source is dispersed in ethanol, it is subsequently adding the pretreated MCM-41 molecular sieve that step one obtains, stirring 5min～10min, then at supersonic frequency be 28kHz～40kHz when supersound process 10min～30min, then deionized water it is added dropwise over, at room temperature stir 1.5h～2.5h, then ageing 10h～14h, place into the oil bath that temperature is 35～45 DEG C to be stirred to water and ethanol and volatilize completely, then dry 3h～5h when temperature is 90～110 DEG C, obtains white solid; The ratio of the quality in described organic titanium source and the volume of ethanol is 1.53g:(10～50) mL; The mass ratio of the pretreated MCM-41 molecular sieve that described organic titanium source and step one obtain is (5～30): 100; The volume ratio of described deionized water and ethanol is (0.018～0.09): 1;
Three, the white solid obtained in step 2 is placed in Muffle furnace, is 150～600 DEG C of calcining 3h～5h in temperature, obtains Ti/MCM-41 molecular sieve.
2. the preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity according to claim 1, it is characterised in that in step one temperature be under 500 DEG C～550 DEG C conditions calcining 4h, obtain pretreated MCM-41 molecular sieve.
3. the preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity according to claim 1, it is characterised in that the organic titanium source described in step 2 is butyl titanate, tetraethyl titanate or isopropyl titanate.
4. the preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity according to claim 1, it is characterised in that the ratio of the quality in the organic titanium source described in step 2 and the volume of ethanol is 1.53g:(20～40) mL.
5. the preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity according to claim 1, it is characterised in that in step 2 in supersonic frequency is 30kHz when supersound process 20min.
6. the preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity according to claim 1, it is characterized in that step 2 at room temperature stirs 2h, then ageing 12h, places into stir in the oil bath that temperature is 40 DEG C to water and ethanol and volatilizees completely.
7. the preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity according to claim 1, it is characterised in that dry 4h in step 2 when temperature is 100 DEG C.
8. the preparation method of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity according to claim 1, it is characterised in that be 350 DEG C in temperature in step 3 and calcine 4h, obtain Ti/MCM-41 molecular sieve.
9. the application of a Ti/MCM-41 molecular sieve with catalytic oxidation activity, it is characterised in that the oxidation sweetening reaction of the simulated oil system that it is sulfur containing species with dibenzothiophenes that a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity is applied to.
10. the application of a kind of Ti/MCM-41 molecular sieve with catalytic oxidation activity according to claim 9, it is characterised in that the described simulated oil in simulated oil system is normal octane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511008942.5A CN105664998A (en) | 2015-12-28 | 2015-12-28 | Preparation method for Ti/MCM-41 molecular sieve having catalytically oxidizing activity and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511008942.5A CN105664998A (en) | 2015-12-28 | 2015-12-28 | Preparation method for Ti/MCM-41 molecular sieve having catalytically oxidizing activity and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105664998A true CN105664998A (en) | 2016-06-15 |
Family
ID=56297852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511008942.5A Pending CN105664998A (en) | 2015-12-28 | 2015-12-28 | Preparation method for Ti/MCM-41 molecular sieve having catalytically oxidizing activity and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105664998A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152722A (en) * | 2019-05-30 | 2019-08-23 | 广东石油化工学院 | A method of synthesis zeolite support type composite catalyst is assisted using polyvinylpyrrolidone |
| CN114832800A (en) * | 2022-06-06 | 2022-08-02 | 宁波大学 | Solid phase micro-extraction probe, preparation method and application thereof in biogenic amine detection |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002090468A1 (en) * | 2001-05-09 | 2002-11-14 | Solvay (Société Anonyme) | Method for desulphurization and/or denitrogenation of a hydrocarbon mixture |
| CN102847548A (en) * | 2012-08-25 | 2013-01-02 | 东北石油大学 | Method for preparing hydrodesulfurization catalyst for oil product under mild condition |
| CN104383959A (en) * | 2014-10-31 | 2015-03-04 | 哈尔滨工业大学 | Preparing method and application of titaniferous mesoporous Y-type molecular sieve with catalytic oxidation activity |
-
2015
- 2015-12-28 CN CN201511008942.5A patent/CN105664998A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002090468A1 (en) * | 2001-05-09 | 2002-11-14 | Solvay (Société Anonyme) | Method for desulphurization and/or denitrogenation of a hydrocarbon mixture |
| CN102847548A (en) * | 2012-08-25 | 2013-01-02 | 东北石油大学 | Method for preparing hydrodesulfurization catalyst for oil product under mild condition |
| CN104383959A (en) * | 2014-10-31 | 2015-03-04 | 哈尔滨工业大学 | Preparing method and application of titaniferous mesoporous Y-type molecular sieve with catalytic oxidation activity |
Non-Patent Citations (2)
| Title |
|---|
| 尹锋等: ""TiO2-MCM-41的制备表征及选择性吸附脱硫研究"", 《石油化工高等学校学报》 * |
| 王广建等: ""Ti-MCM-41介孔分子筛催化氧化噻吩性能"", 《化工进展》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152722A (en) * | 2019-05-30 | 2019-08-23 | 广东石油化工学院 | A method of synthesis zeolite support type composite catalyst is assisted using polyvinylpyrrolidone |
| CN110152722B (en) * | 2019-05-30 | 2022-04-12 | 广东石油化工学院 | Method for assisting in synthesizing zeolite molecular sieve supported composite catalyst by utilizing polyvinylpyrrolidone |
| CN114832800A (en) * | 2022-06-06 | 2022-08-02 | 宁波大学 | Solid phase micro-extraction probe, preparation method and application thereof in biogenic amine detection |
| CN114832800B (en) * | 2022-06-06 | 2023-08-01 | 宁波大学 | Solid-phase microextraction probe, preparation method and application thereof in biogenic amine detection |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Beutel et al. | Redox chemistry of Cu/ZSM-5 | |
| Hadjiivanov et al. | Surface species formed after NO adsorption and NO+ O2 coadsorption on ZrO2 and sulfated ZrO2: an FTIR spectroscopic study | |
| CN103240130B (en) | TiO2 / MIL-101 composite catalyst for photocatalytic water splitting and preparation method and applications thereof | |
| CN101274922B (en) | Preparation for epoxypropane | |
| CN104084205B (en) | A kind of preparation method and application thereof of titania nanotube of the iron load with catalytic oxidation activity | |
| CN102921456B (en) | Heterogeneous catalyst, preparation method of heterogeneous catalyst and application of heterogeneous catalyst | |
| CN103657696A (en) | Preparation method of attapulgite-based solid acid catalyst for vegetable fat epoxidation | |
| CN107573516B (en) | Preparation method of vanadium modified metal organic framework material | |
| CN105289732A (en) | MOF supported metal peroxide catalyst | |
| CN105664998A (en) | Preparation method for Ti/MCM-41 molecular sieve having catalytically oxidizing activity and application thereof | |
| CN111097498B (en) | CH 4 -SCR denitration catalyst, preparation method thereof and exhaust gas denitration method | |
| CN111659324B (en) | Ozone catalytic system composite aerogel and preparation method and application thereof | |
| CN114682241B (en) | Titanium dioxide-aluminum oxide composite desulfurization catalyst and preparation method and application thereof | |
| CN111545197A (en) | Ru-ZnO photocatalyst and preparation method and application thereof | |
| CN112044425B (en) | Hydrochloric acid acidified kaolin loaded vanadium oxidation desulfurization catalyst and preparation and application thereof | |
| Sun et al. | Insight into the Role of TiO2 Facets in Photocatalytic Selective Oxidation of p-Xylene | |
| CN111135867B (en) | Metal organic iron complex, polyacid and titanium-silicon molecular sieve composite catalyst and preparation method thereof | |
| CN104383959B (en) | A kind of preparation method and applications of the titanium-containing meso-porous Y type molecular sieve with catalytic oxidation activity | |
| CN103706398A (en) | supported vanadium-substituted phosphotungstic acid catalyst and preparation method and application of catalyst | |
| CN104874420A (en) | Preparation method for titanium-containing hierarchical porous structure mesoporous molecular sieve catalyst | |
| CN111659323B (en) | Composite aerogel functional material and preparation method and application thereof | |
| CN111974408B (en) | Immobilized heterogeneous Fenton catalyst and preparation method and application thereof | |
| CN109550522A (en) | A kind of wet oxidizing catalyst, preparation method and its application handling refinery basic sewage | |
| CN106588539A (en) | Method for preparing ethylene by using modification type platinum catalyst for catalyzing oxidative dehydrogenation of ethane | |
| CN106563494A (en) | Preparation method and applications of modified H-Beta molecular sieve catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160615 |