CN104741151A - Preparation method and application of carbon-doped nanometer compound metal oxide - Google Patents
Preparation method and application of carbon-doped nanometer compound metal oxide Download PDFInfo
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- CN104741151A CN104741151A CN201510154778.2A CN201510154778A CN104741151A CN 104741151 A CN104741151 A CN 104741151A CN 201510154778 A CN201510154778 A CN 201510154778A CN 104741151 A CN104741151 A CN 104741151A
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 compound metal oxide Chemical class 0.000 title abstract 5
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000013178 MIL-101(Cr) Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 57
- 239000002114 nanocomposite Substances 0.000 claims description 57
- 239000000376 reactant Substances 0.000 claims description 56
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- 238000005119 centrifugation Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004587 chromatography analysis Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 20
- 239000010936 titanium Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention discloses a preparation method and application of a carbon-doped nanometer compound metal oxide, relates to a preparation method of a catalyst and application of the catalyst in oxidative desulfurization reaction, and aims to solve the problems of small specific area and low catalytic activity of an existing catalyst. The preparation method comprises the following steps: 1, preparing a solid matter A; 2, preparing MIL-101 (Cr); 3, preparing degassed MIL-101 (Cr); 4, preparing an MIL-101 (Cr)/Ti compound material; and 5, calcining the MIL-101 (Cr)/Ti compound material under a nitrogen atmosphere to obtain the carbon-doped nanometer compound metal oxide. The carbon-doped nanometer compound metal oxide prepared by adopting the preparation method has the relatively high catalytic activity on the oxidative desulfurization reaction, and the conversion rate of dibenzothiophene reaches 90 percent. According to the invention, the preparation method of the carbon-doped nanometer compound metal oxide can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst and the application in oxidation desulfur reaction thereof.
Background technology
Sulfide is ubiquitous pollutant in crude oil.When oil combustion, sulfide can be transformed into oxysulfide, causes the generation of acid rain.Hydrodesulfurization (HDS) is the common method of desulfurization in fuel, but this method needs HTHP, and lower for some aromatics sulfide (as dibenzothiophenes etc.) efficiency.Oxidation sweetening (ODS) can be good at addressing this problem.
Metal-organic framework materials (MOFs) a kind ofly coordinates by metal ion and organic ligand the porous crystalline formed.The material with carbon element prepared based on MOF recently arouses great concern because of the pore structure that its high-ratio surface sum is controlled.At present, the TiO of anatase phase has been proved
2there is good catalytic activity in oxidation sweetening, but nano level TiO
2easily assemble in reaction system, bad dispersibility, can not contact with reactant well, thus catalytic activity is not high.For addressing this problem, attempt TiO
2load on the carbon of specific area more much higher hole, the activated centre of oxidation desulfur reaction not only can be provided, and the pore structure of porous carbon can be utilized, make titanium elements have good dispersiveness, thus obtain a kind of heterogeneous catalyst, greatly improve the reactivity of oxidation sweetening.
Summary of the invention
The object of the invention is to solve existing catalyst and there is the problem that specific area is little and catalytic activity is low, and a kind of preparation method and application of carbon-doped nano composite metal oxide are provided.
A preparation method for carbon-doped nano composite metal oxide, completes according to the following steps:
One, in autoclave, Cr (NO is added
3)
39H
2o, terephthalic acid (TPA) and deionized water, seal autoclave after mixing; The autoclave of sealing being put into temperature is leave standstill 15h ~ 20h in the baking oven of 200 DEG C ~ 250 DEG C; Carry out centrifugation again, then the solid matter that uses deionized water, methyl alcohol and acetone to clean successively to obtain after centrifugation 1 time ~ 2 times, obtain solid matter A;
Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of deionized water are 1g:(8mL ~ 20mL);
Cr (NO described in step one
3)
39H
2the mass ratio of O and terephthalic acid (TPA) is 1:(0.2 ~ 0.8);
Two, solid matter A is joined N, ultrasonic process 5min ~ 15min in dinethylformamide, then carry out centrifugation, the solid matter obtained after using washed with methanol centrifugation 2 times ~ 3 times, dry 6h ~ 8h at temperature is 50 DEG C ~ 70 DEG C, obtains MIL-101 (Cr) again;
The quality of the solid matter A described in step 2 and the volume ratio of DMF are 1g:(20mL ~ 40mL);
Three, be leave standstill 10h ~ 14h in the vacuum drying chamber of 100 DEG C ~ 200 DEG C in temperature by MIL-101 (Cr), obtain degassed after MIL-101 (Cr);
Four, butyl titanate is joined in absolute ethyl alcohol, add again degassed after MIL-101 (Cr), ultrasonic process 10min ~ 15min again, then be 50 DEG C ~ 70 DEG C dry 15h ~ 22h in temperature, obtain MIL-101 (Cr)/Ti composite;
The quality of the butyl titanate described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(0.8mL ~ 1.3mL);
The quality of MIL-101 (Cr) after degassed described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(1mL ~ 2.5mL);
Five, MIL-101 (Cr)/Ti composite is calcined 4h ~ 6h under temperature is 500 DEG C ~ 700 DEG C and nitrogen atmosphere, obtain carbon-doped nano composite metal oxide.
A kind of carbon-doped nano composite metal oxide is applied in oxidation desulfur reaction and carries out according to the following steps:
One, dibenzothiophenes is dissolved in normal octane, then adds carbon-doped nano composite metal oxide, then be 50 DEG C ~ 60 DEG C and mixing speed in temperature be that 800r/min ~ 1200r/min lower magnetic force stirs 20min ~ 30min, obtain reactant liquor; Extract reaction solution 0.5mL ~ 1mL, use the initial concentration C of dibenzothiophenes in gas chromatographic analysis reactant liquor
0;
The mass ratio of the dibenzothiophenes described in step one and normal octane is 5.75 × 10
-3: 1;
The mass ratio of the dibenzothiophenes described in step one and carbon-doped nano composite metal oxide is (0.5 ~ 3): 1;
Two, add isopropyl benzene hydroperoxide in the reactant liquor obtained in step one, obtain the reactant liquor after adding isopropyl benzene hydroperoxide; Get the reactant liquor adding any time after isopropyl benzene hydroperoxide respectively; Gas chromatographic analysis is used to add the concentration C of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide
i;
In reactant liquor described in step 2, the mol ratio of dibenzothiophenes and isopropyl benzene hydroperoxide is 1:6;
Three, following formulae discovery is utilized to add the conversion ratio of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide;
In above-mentioned formula:
C
0for the initial concentration of dibenzothiophenes in reactant liquor;
C
ifor add any time after isopropyl benzene hydroperoxide reactant liquor in the concentration C of dibenzothiophenes
i;
The degree of conversion alpha % of the concentration of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide is gone out to add according to above-mentioned formulae discovery.
Advantage of the present invention:
One, the present invention be directed to oxidation desulfur reaction and the preparation method of the high-activity carbon dopen Nano composite metal oxide designed; The present invention, by the method for butyl titanate by wet impregnation, is combined with the special skeleton structure of MIL-101 (Cr), obtains the MIL-101 (Cr) of load Ti, at N
2the lower carbonization of protection, obtains carbon-doped nano composite metal oxide;
Two, the carbon-doped nano composite metal oxide that obtains of the present invention is higher for the catalytic activity of oxidation desulfur reaction, and the conversion ratio of dibenzothiophenes reaches 90%; And this method avoid and directly calcine the structure collapse caused in atmosphere, its material obtained still partly can retain the skeleton structure of MIL-101 (Cr);
Three, the specific area of carbon-doped nano composite metal oxide that the present invention obtains is 200m
2/ g ~ 300m
2/ g.
The present invention can obtain a kind of preparation method of carbon-doped nano composite metal oxide.
Accompanying drawing explanation
Fig. 1 is XRD diffraction pattern; In Fig. 1,1 is TiO
2xRD curve, 2 is the XRD curve of the carbon-doped nano composite metal oxide that test two obtains;
Fig. 2 is adsorption curve; In Fig. 2,1 is the Cr that test one obtains
2o
3the BET adsorption curve of catalyst, 2 is the BET adsorption curve of the carbon-doped nano composite metal oxide that test two obtains;
Fig. 3 is the conversion rate curve of DBT, and in Fig. 3,1 is the Cr that service test one obtains
2o
3the conversion rate curve of DBT after catalyst, 2 is the conversion rate curve of DBT after the carbon-doped nano composite metal oxide that obtains of service test two.
Detailed description of the invention
Detailed description of the invention one: present embodiment is that a kind of preparation method of carbon-doped nano composite metal oxide completes according to the following steps:
One, in autoclave, Cr (NO is added
3)
39H
2o, terephthalic acid (TPA) and deionized water, seal autoclave after mixing; The autoclave of sealing being put into temperature is leave standstill 15h ~ 20h in the baking oven of 200 DEG C ~ 250 DEG C; Carry out centrifugation again, then the solid matter that uses deionized water, methyl alcohol and acetone to clean successively to obtain after centrifugation 1 time ~ 2 times, obtain solid matter A;
Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of deionized water are 1g:(8mL ~ 20mL);
Cr (NO described in step one
3)
39H
2the mass ratio of O and terephthalic acid (TPA) is 1:(0.2 ~ 0.8);
Two, solid matter A is joined N, ultrasonic process 5min ~ 15min in dinethylformamide, then carry out centrifugation, the solid matter obtained after using washed with methanol centrifugation 2 times ~ 3 times, dry 6h ~ 8h at temperature is 50 DEG C ~ 70 DEG C, obtains MIL-101 (Cr) again;
The quality of the solid matter A described in step 2 and the volume ratio of DMF are 1g:(20mL ~ 40mL);
Three, be leave standstill 10h ~ 14h in the vacuum drying chamber of 100 DEG C ~ 200 DEG C in temperature by MIL-101 (Cr), obtain degassed after MIL-101 (Cr);
Four, butyl titanate is joined in absolute ethyl alcohol, add again degassed after MIL-101 (Cr), ultrasonic process 10min ~ 15min again, then be 50 DEG C ~ 70 DEG C dry 15h ~ 22h in temperature, obtain MIL-101 (Cr)/Ti composite;
The quality of the butyl titanate described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(0.8mL ~ 1.3mL);
The quality of MIL-101 (Cr) after degassed described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(1mL ~ 2.5mL);
Five, MIL-101 (Cr)/Ti composite is calcined 4h ~ 6h under temperature is 500 DEG C ~ 700 DEG C and nitrogen atmosphere, obtain carbon-doped nano composite metal oxide.
The advantage of present embodiment:
One, present embodiment is the preparation method of the high-activity carbon dopen Nano composite metal oxide designed for oxidation desulfur reaction; Present embodiment, by the method for butyl titanate by wet impregnation, is combined with the special skeleton structure of MIL-101 (Cr), obtains the MIL-101 (Cr) of load Ti, at N
2the lower carbonization of protection, obtains carbon-doped nano composite metal oxide;
Two, the carbon-doped nano composite metal oxide that obtains of present embodiment is higher for the catalytic activity of oxidation desulfur reaction, and the conversion ratio of dibenzothiophenes reaches 90%; And this method avoid and directly calcine the structure collapse caused in atmosphere, its material obtained still partly can retain the skeleton structure of MIL-101 (Cr);
Three, the specific area of carbon-doped nano composite metal oxide that present embodiment obtains is 200m
2/ g ~ 300m
2/ g.
Present embodiment can obtain a kind of preparation method of carbon-doped nano composite metal oxide.
Detailed description of the invention two: present embodiment and detailed description of the invention one difference are: the Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of deionized water are 1g:(8mL ~ 10mL).Other steps are identical with detailed description of the invention one.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two difference is: the Cr (NO described in step one
3)
39H
2the mass ratio of O and terephthalic acid (TPA) is 1:(0.2 ~ 0.4).Other steps 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 difference is: the power of the ultrasonic process described in step 2 is 160W ~ 200W.Other steps are identical with detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four difference is: the quality of the solid matter A described in step 2 and the volume ratio of DMF are 1g:(20mL ~ 30mL).Other steps are identical with detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five difference is: the power of the ultrasonic process described in step 4 is 160W ~ 200W.Other steps are identical with detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six difference is: the quality of the butyl titanate described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(0.8mL ~ 1mL).Other steps are identical with detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven difference is: the quality of MIL-101 (Cr) after degassed described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(1mL ~ 1.5mL).Other steps are identical with detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight difference is: in step 5, MIL-101 (Cr)/Ti composite is calcined 4h ~ 5h under temperature is 500 DEG C ~ 550 DEG C and nitrogen atmosphere, obtain carbon-doped nano composite metal oxide.Other steps are identical with detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment is that a kind of carbon-doped nano composite metal oxide is applied in oxidation desulfur reaction is carry out according to the following steps:
One, dibenzothiophenes is dissolved in normal octane, then adds carbon-doped nano composite metal oxide, then be 50 DEG C ~ 60 DEG C and mixing speed in temperature be that 800r/min ~ 1200r/min lower magnetic force stirs 20min ~ 30min, obtain reactant liquor; Extract reaction solution 0.5mL ~ 1mL, use the initial concentration C of dibenzothiophenes in gas chromatographic analysis reactant liquor
0;
The mass ratio of the dibenzothiophenes described in step one and normal octane is 5.75 × 10
-3: 1;
The mass ratio of the dibenzothiophenes described in step one and carbon-doped nano composite metal oxide is (0.5 ~ 3): 1;
Two, add isopropyl benzene hydroperoxide in the reactant liquor obtained in step one, obtain the reactant liquor after adding isopropyl benzene hydroperoxide; Get the reactant liquor adding any time after isopropyl benzene hydroperoxide respectively; Gas chromatographic analysis is used to add the concentration C of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide
i;
In reactant liquor described in step 2, the mol ratio of dibenzothiophenes and isopropyl benzene hydroperoxide is 1:6;
Three, following formulae discovery is utilized to add the conversion ratio of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide;
In above-mentioned formula:
C
0for the initial concentration of dibenzothiophenes in reactant liquor;
C
ifor add any time after isopropyl benzene hydroperoxide reactant liquor in the concentration C of dibenzothiophenes
i;
The degree of conversion alpha % of the concentration of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide is gone out to add according to above-mentioned formulae discovery.
The advantage of present embodiment:
One, present embodiment is the preparation method of the high-activity carbon dopen Nano composite metal oxide designed for oxidation desulfur reaction; Present embodiment, by the method for butyl titanate by wet impregnation, is combined with the special skeleton structure of MIL-101 (Cr), obtains the MIL-101 (Cr) of load Ti, at N
2the lower carbonization of protection, obtains carbon-doped nano composite metal oxide;
Two, the carbon-doped nano composite metal oxide that obtains of present embodiment is higher for the catalytic activity of oxidation desulfur reaction, and the conversion ratio of dibenzothiophenes reaches 90%; And this method avoid and directly calcine the structure collapse caused in atmosphere, its material obtained still partly can retain the skeleton structure of MIL-101 (Cr);
Three, the specific area of carbon-doped nano composite metal oxide that present embodiment obtains is 200m
2/ g ~ 300m
2/ g.
Adopt following verification experimental verification beneficial effect of the present invention:
Cr is prepared in test one: dinectly bruning MIL-101 (Cr)
2o
3the preparation method of catalyst, completes according to the following steps:
One, in 25mL autoclave, 1.8g Cr (NO is added
3)
39H
2o, 0.747g terephthalic acid (TPA) and 18mL deionized water, seal autoclave after mixing; The autoclave of sealing being put into temperature is leave standstill 18h in the baking oven of 218 DEG C; Carry out centrifugation again, then the solid matter that uses deionized water, methyl alcohol and acetone to clean successively to obtain after centrifugation 1 time, obtain solid matter A;
Two, 1g solid matter A is joined 20mL N, ultrasonic process 10min in dinethylformamide, then carry out centrifugation, the solid matter obtained after using washed with methanol centrifugation 2 times, dry 8h at temperature is 65 DEG C, obtains MIL-101 (Cr) again;
The power of the ultrasonic process described in step 2 is 200W;
Three, be leave standstill 12h in the vacuum drying chamber of 150 DEG C in temperature by MIL-101 (Cr), obtain degassed after MIL-101 (Cr);
Four, the MIL-101 (Cr) after 0.3g is degassed calcines 5.5h under temperature is 550 DEG C and air atmosphere, obtains Cr
2o
3catalyst.
Test two: a kind of preparation method of carbon-doped nano composite metal oxide specifically completes according to the following steps:
One, in 25mL autoclave, 1.8g Cr (NO is added
3)
39H
2o, 0.747g terephthalic acid (TPA) and 18mL deionized water, seal autoclave after mixing; The autoclave of sealing being put into temperature is leave standstill 18h in the baking oven of 218 DEG C; Carry out centrifugation again, then the solid matter that uses deionized water, methyl alcohol and acetone to clean successively to obtain after centrifugation 1 time, obtain solid matter A;
Two, 1g solid matter A is joined 20mL N, ultrasonic process 10min in dinethylformamide, then carry out centrifugation, the solid matter obtained after using washed with methanol centrifugation 2 times, dry 8h at temperature is 65 DEG C, obtains MIL-101 (Cr) again;
The power of the ultrasonic process described in step 2 is 200W;
Three, be leave standstill 12h in the vacuum drying chamber of 150 DEG C in temperature by MIL-101 (Cr), obtain degassed after MIL-101 (Cr);
Four, 0.4270g butyl titanate is joined in 0.5mL absolute ethyl alcohol, then add 0.3g degassed after MIL-101 (Cr), more ultrasonic process 15min, then be 65 DEG C of dry 20h in temperature, obtains MIL-101 (Cr)/Ti composite;
The power of the ultrasonic process described in step 4 is 200W;
Five, 0.3gMIL-101 (Cr)/Ti composite is calcined 5.5h under temperature is 550 DEG C and nitrogen atmosphere, obtain carbon-doped nano composite metal oxide.
Fig. 1 is XRD diffraction pattern; In Fig. 1,1 is TiO
2xRD curve, 2 is the XRD curve of the carbon-doped nano composite metal oxide that test two obtains.As can be seen from Figure 1, testing titanium elements in the two carbon-doped nano composite metal oxides obtained is exist with the form of titanium dioxide.
Fig. 2 is adsorption curve; In Fig. 2,1 is the Cr that test one obtains
2o
3the BET adsorption curve of catalyst, 2 is the BET adsorption curve of the carbon-doped nano composite metal oxide that test two obtains.
As can be seen from Figure 2, the TiO of the carbon-doped nano composite metal oxide load that two obtain is tested
2still partly can retain the pore structure of MIL-101 (Cr), and test a Cr obtained
2o
3the pore structure of catalyst caves in completely.
Test three: 57.5mg dibenzothiophenes is dissolved in 10g normal octane, then the Cr adding that test one obtains
2o
3catalyst, then be 55 DEG C and mixing speed in temperature be that 1000r/min lower magnetic force stirs 25min, obtain reactant liquor; Extract reaction solution 0.5mL, use the initial concentration C of dibenzothiophenes in gas chromatographic analysis reactant liquor
0;
The mass ratio of the dibenzothiophenes described in step one and carbon-doped nano composite metal oxide is 1.15:1;
Two, add isopropyl benzene hydroperoxide in the reactant liquor obtained in step one, obtain the reactant liquor after adding isopropyl benzene hydroperoxide; The reactant liquor added after isopropyl benzene hydroperoxide of 20min, 30min, 60min, 90min and 120min is answered in negate respectively, uses the concentration C adding dibenzothiophenes in the reactant liquor after isopropyl benzene hydroperoxide of gas-chromatography analytical reactions 20min, 30min, 60min, 90min and 120min respectively
i;
In reactant liquor described in step 2, the mol ratio of dibenzothiophenes and isopropyl benzene hydroperoxide is 1:6;
Three, the conversion ratio adding dibenzothiophenes in the reactant liquor after isopropyl benzene hydroperoxide of the reaction of following formulae discovery 20min, 30min, 60min, 90min and 120min is utilized;
In above-mentioned formula:
C
0for the initial concentration of dibenzothiophenes in reactant liquor;
C
ifor reacting the concentration C adding dibenzothiophenes in the reactant liquor after isopropyl benzene hydroperoxide of 20min, 30min, 60min, 90min and 120min
i;
The degree of conversion alpha adding the concentration of dibenzothiophenes in the reactant liquor after isopropyl benzene hydroperoxide of 20min, 30min, 60min, 90min and 120min is gone out to react according to above-mentioned formulae discovery
20, α
30, α
60, α
90and α
120, as shown in curve in Fig. 31.
Test four: 57.5mg dibenzothiophenes is dissolved in 10g normal octane, then the carbon-doped nano composite metal oxide adding that test two obtains, then be 55 DEG C and mixing speed in temperature be that 1000r/min lower magnetic force stirs 25min, obtain reactant liquor; Extract reaction solution 0.5mL, use the initial concentration C of dibenzothiophenes in gas chromatographic analysis reactant liquor
0;
The mass ratio of the dibenzothiophenes described in step one and carbon-doped nano composite metal oxide is 1.15:1;
Two, add isopropyl benzene hydroperoxide in the reactant liquor obtained in step one, obtain the reactant liquor after adding isopropyl benzene hydroperoxide; The reactant liquor added after isopropyl benzene hydroperoxide of 20min, 30min, 60min, 90min and 120min is answered in negate respectively, uses the concentration C adding dibenzothiophenes in the reactant liquor after isopropyl benzene hydroperoxide of gas-chromatography analytical reactions 20min, 30min, 60min, 90min and 120min respectively
i;
In reactant liquor described in step 2, the mol ratio of dibenzothiophenes and isopropyl benzene hydroperoxide is 1:6;
Three, the conversion ratio adding dibenzothiophenes in the reactant liquor after isopropyl benzene hydroperoxide of the reaction of following formulae discovery 20min, 30min, 60min, 90min and 120min is utilized;
In above-mentioned formula:
C
0for the initial concentration of dibenzothiophenes in reactant liquor;
C
ifor reacting the concentration C adding dibenzothiophenes in the reactant liquor after isopropyl benzene hydroperoxide of 20min, 30min, 60min, 90min and 120min
i;
The degree of conversion alpha adding the concentration of dibenzothiophenes in the reactant liquor after isopropyl benzene hydroperoxide of 20min, 30min, 60min, 90min and 120min is gone out to react according to above-mentioned formulae discovery
20, α
30, α
60, α
90and α
120, as shown in curve in Fig. 32.
Fig. 3 is the conversion rate curve of DBT, and in Fig. 3,1 is the Cr that service test one obtains
2o
3the conversion rate curve of DBT after catalyst, 2 is the conversion rate curve of DBT after the carbon-doped nano composite metal oxide that obtains of service test two.
As can be seen from Figure 3, the Transformation efficiency is up to 90 % of dibenzothiophenes DBT, the Cr that service test one obtains after the carbon-doped nano composite metal oxide that service test two obtains
2o
3after catalyst, the conversion ratio of DBT is 60%.
Claims (10)
1. a preparation method for carbon-doped nano composite metal oxide, is characterized in that a kind of preparation method of carbon-doped nano composite metal oxide completes according to the following steps:
One, in autoclave, Cr (NO is added
3)
39H
2o, terephthalic acid (TPA) and deionized water, seal autoclave after mixing; The autoclave of sealing being put into temperature is leave standstill 15h ~ 20h in the baking oven of 200 DEG C ~ 250 DEG C; Carry out centrifugation again, then the solid matter that uses deionized water, methyl alcohol and acetone to clean successively to obtain after centrifugation 1 time ~ 2 times, obtain solid matter A;
Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of deionized water are 1g:(8mL ~ 20mL);
Cr (NO described in step one
3)
39H
2the mass ratio of O and terephthalic acid (TPA) is 1:(0.2 ~ 0.8);
Two, solid matter A is joined N, ultrasonic process 5min ~ 15min in dinethylformamide, then carry out centrifugation, the solid matter obtained after using washed with methanol centrifugation 2 times ~ 3 times, dry 6h ~ 8h at temperature is 50 DEG C ~ 70 DEG C, obtains MIL-101 (Cr) again;
The quality of the solid matter A described in step 2 and the volume ratio of DMF are 1g:(20mL ~ 40mL);
Three, be leave standstill 10h ~ 14h in the vacuum drying chamber of 100 DEG C ~ 200 DEG C in temperature by MIL-101 (Cr), obtain degassed after MIL-101 (Cr);
Four, butyl titanate is joined in absolute ethyl alcohol, add again degassed after MIL-101 (Cr), ultrasonic process 10min ~ 15min again, then be 50 DEG C ~ 70 DEG C dry 15h ~ 22h in temperature, obtain MIL-101 (Cr)/Ti composite;
The quality of the butyl titanate described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(0.8mL ~ 1.3mL);
The quality of MIL-101 (Cr) after degassed described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(1mL ~ 2.5mL);
Five, MIL-101 (Cr)/Ti composite is calcined 4h ~ 6h under temperature is 500 DEG C ~ 700 DEG C and nitrogen atmosphere, obtain carbon-doped nano composite metal oxide.
2. the preparation method of a kind of carbon-doped nano composite metal oxide according to claim 1, is characterized in that the Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of deionized water are 1g:(8mL ~ 10mL).
3. the preparation method of a kind of carbon-doped nano composite metal oxide according to claim 1, is characterized in that the Cr (NO described in step one
3)
39H
2the mass ratio of O and terephthalic acid (TPA) is 1:(0.2 ~ 0.4).
4. the preparation method of a kind of carbon-doped nano composite metal oxide according to claim 1, is characterized in that the power of the ultrasonic process described in step 2 is 160W ~ 200W.
5. the preparation method of a kind of carbon-doped nano composite metal oxide according to claim 1, is characterized in that the quality of the solid matter A described in step 2 and the volume ratio of DMF are 1g:(20mL ~ 30mL).
6. the preparation method of a kind of carbon-doped nano composite metal oxide according to claim 1, is characterized in that the power of the ultrasonic process described in step 4 is 160W ~ 200W.
7. the preparation method of a kind of carbon-doped nano composite metal oxide according to claim 1, is characterized in that the quality of the butyl titanate described in step 4 and the volume ratio of absolute ethyl alcohol are 1g:(0.8mL ~ 1mL).
8. the preparation method of a kind of carbon-doped nano composite metal oxide according to claim 1, the quality of MIL-101 (Cr) after to it is characterized in that described in step 4 degassed and the volume ratio of absolute ethyl alcohol are 1g:(1mL ~ 1.5mL).
9. according to the preparation method of a kind of carbon-doped nano composite metal oxide according to claim 1, it is characterized in that, in step 5, MIL-101 (Cr)/Ti composite is calcined 4h ~ 5h under temperature is 500 DEG C ~ 550 DEG C and nitrogen atmosphere, obtain carbon-doped nano composite metal oxide.
10. an application for carbon-doped nano composite metal oxide, is characterized in that a kind of carbon-doped nano composite metal oxide is applied in oxidation desulfur reaction and carries out according to the following steps:
One, dibenzothiophenes is dissolved in normal octane, then adds carbon-doped nano composite metal oxide, then be 50 DEG C ~ 60 DEG C and mixing speed in temperature be that 800r/min ~ 1200r/min lower magnetic force stirs 20min ~ 30min, obtain reactant liquor; Extract reaction solution 0.5mL ~ 1mL, use the initial concentration C of dibenzothiophenes in gas chromatographic analysis reactant liquor
0;
The mass ratio of the dibenzothiophenes described in step one and normal octane is 5.75 × 10
-3: 1;
The mass ratio of the dibenzothiophenes described in step one and carbon-doped nano composite metal oxide is (0.5 ~ 3): 1;
Two, add isopropyl benzene hydroperoxide in the reactant liquor obtained in step one, obtain the reactant liquor after adding isopropyl benzene hydroperoxide; Get the reactant liquor adding any time after isopropyl benzene hydroperoxide respectively; Gas chromatographic analysis is used to add the concentration C of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide
i;
In reactant liquor described in step 2, the mol ratio of dibenzothiophenes and isopropyl benzene hydroperoxide is 1:6;
Three, following formulae discovery is utilized to add the conversion ratio of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide;
In above-mentioned formula:
C
0for the initial concentration of dibenzothiophenes in reactant liquor;
C
ifor add any time after isopropyl benzene hydroperoxide reactant liquor in the concentration C of dibenzothiophenes
i;
The degree of conversion alpha % of the concentration of dibenzothiophenes in the reactant liquor of any time after isopropyl benzene hydroperoxide is gone out to add according to above-mentioned formulae discovery.
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| CN114460150A (en) * | 2022-02-09 | 2022-05-10 | 福州市第二医院（福建省福州中西医结合医院、福州市职业病医院） | Unmarked DNA photoelectrochemical detection method based on MOFs composite material |
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| CN114460150B (en) * | 2022-02-09 | 2023-04-11 | 福州市第二医院（福建省福州中西医结合医院、福州市职业病医院） | Unmarked DNA photoelectrochemical detection method based on MOFs composite material |
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