CN104475165A - Preparation method of oxidative desulfurization catalyst - Google Patents
Preparation method of oxidative desulfurization catalyst Download PDFInfo
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- CN104475165A CN104475165A CN201410765880.1A CN201410765880A CN104475165A CN 104475165 A CN104475165 A CN 104475165A CN 201410765880 A CN201410765880 A CN 201410765880A CN 104475165 A CN104475165 A CN 104475165A
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Abstract
The invention discloses a preparation method of an oxidative desulfurization catalyst, and relates to a preparation method of the catalyst, which aims to solve the problem that the preparation method of the existing oxidative desulfurization catalyst is complex in preparation process. The preparation method comprises the following steps of firstly, preparing a MIL-101(Cr) precursor solution, then carrying out hydrothermal reaction, then adding the precursor solution into a NH4F solution, and heating and stirring; and then degassing under a vacuum condition, and adding a titanium source so as to obtain the oxidative desulfurization catalyst. According to the preparation method, a metal organic framework material (MOFs) and a titanium element are combined together, so that not only can an active center of the oxidative desulfurization reaction be provided, but also a porous metal oxide can be obtained by utilizing a special MOFs framework structure, so that the titanium element has very good dispersity, and the reaction activity of 30%-40% of oxidative desulfurization is improved. According to the invention, the preparation method of the oxidative desulfurization catalyst can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst.
In recent years, population in the world is growing, and the dependence of people to both privately and publicly owned's communications and transportation is increasing.Automobile, in the tail gas of the vehicle emissions such as aircraft, atmosphere pollution gets more and more.SO
2become a kind of main pollutant.This is because containing different types of containing S compound (thiophene, sulfide, disulphide, benzene thiophene) in a large number in these transport fuels (such as, diesel oil), these can burn containing S compound and generate SO
2.In nearest environmental index regulation liquid fuel must at below 10ppm containing S content.This makes many industrial process start then pays close attention to the desulphurization problem of liquid fuel.
Current existing sulfur method mainly contains three kinds, hydrodesulfurization (HDS), adsorption desulfurize (ADS) and oxidation sweetening (ODS).Although HDS and ADS has been widely used in desulfurization, the removal efficiency for aromatic series thiophene-type sulfide (as dibenzo thiophene, thiophene) has obviously been not so good as ODS.ODS reaction condition is gentle, does not need hydrogenation, and can carry out at ambient pressure.Therefore, removing for thiophene-type sulfide, ODS has good development prospect.
Metal-organic framework materials (MOFs) is combined with titanium elements, the activated centre of oxidation desulfur reaction not only can be provided, and the special skeleton structure of MOFs can be utilized to obtain porous metal oxide, make titanium elements have good dispersiveness, thus greatly improve the reactivity of oxidation sweetening.
Summary of the invention
The object of the invention is the problem that will solve existing oxidation-desulfurizing catalyst preparation process complexity, and a kind of preparation method of oxidation-desulfurizing catalyst is easily provided.
A preparation method for oxidation-desulfurizing catalyst, specifically completes according to the following steps:
One, MIL-101 (Cr) precursor solution is prepared: by Cr (NO
3)
39H
2o and terephthalic acid (TPA) join in distilled water, under room temperature and ultrasonic power be ultrasonic disperse 30min ~ 60min under the condition of 160W ~ 200W, obtain the suspension that pH value is 2 ~ 4; By pH value be again 2 ~ 4 suspension join in the polytetrafluoroethyllining lining of autoclave, the autoclave of sealing being put into temperature is heat 16h ~ 18h in the baking oven of 200 DEG C ~ 220 DEG C again, obtains MIL-101 (Cr) precursor solution that pH value is 0.1 ~ 1;
Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of distilled water are 1g:(7mL ~ 16mL);
The quality of the terephthalic acid (TPA) described in step one and the volume ratio of distilled water are 1g:(12mL ~ 80mL);
Two, by pH value be 0.1 ~ 1 MIL-101 (Cr) precursor solution filter, obtain solid matter A; Again by solid matter A dry 6h ~ 8h at temperature is 60 DEG C ~ 80 DEG C, obtain dried solid matter A; Dried solid matter A is joined in absolute ethyl alcohol, then at temperature is 60 DEG C ~ 80 DEG C hydrothermal treatment consists 20h ~ 30h, then to filter, obtain solid matter B; Re-use absolute ethyl alcohol and washing carried out 3 times ~ 4 times to solid matter B, then at temperature is 60 DEG C ~ 80 DEG C dry 1h ~ 2h, obtain dried solid matter B;
The quality of dried solid matter A described in step 2 and the volume ratio of absolute ethyl alcohol are 1g:(40mL ~ 50mL);
Three, dried solid matter B is joined the NH that concentration is 1mol/L ~ 2mol/L
4in F solution, then stir 20h ~ 30h under temperature is 60 DEG C ~ 80 DEG C and mixing speed is 800r/min ~ 1200r/min, then filter, obtain solid matter C; Re-using temperature is that the distilled water of 25 DEG C ~ 30 DEG C carries out washing 3 ~ 4 times to solid matter C, then at temperature is 60 DEG C ~ 80 DEG C dry 6h ~ 8h, obtain dried solid matter C;
The quality of the dried solid matter B described in step 3 and concentration are the NH of 1mol/L ~ 2mol/L
4the volume ratio of F solution is 1g:(30mL ~ 50mL);
Four, by dried solid matter C in temperature be 150 DEG C ~ 200 DEG C and vacuum condition under carry out degassed 10h ~ 12h; Obtain degassed after solid matter C;
Five, titanium source is mixed with solvent, obtain titanium source solution; By obtain in step 4 degassed after solid matter C join in the solution of titanium source, at temperature is 60 DEG C ~ 80 DEG C, heat 10h ~ 20h after mixing, then calcine 2h ~ 6h at temperature be 400 DEG C ~ 600 DEG C, obtain oxidation-desulfurizing catalyst;
In titanium source solution described in step 5, the quality in titanium source and the volume ratio of solvent are 1g:(0.4mL ~ 0.5mL);
In the quality of the solid matter C after degassed described in step 5 and titanium source solution, the mass ratio of titanium atom is 1:(0.1 ~ 0.5).
Advantage of the present invention: metal-organic framework materials (MOFs) combines with titanium elements by the present invention, the activated centre of oxidation desulfur reaction not only can be provided, and the special skeleton structure of MOFs can be utilized to obtain porous metal oxide, make titanium elements have good dispersiveness, thus improve the reactivity of 30% ~ 40% oxidation sweetening.
The present invention can obtain a kind of preparation method of oxidation-desulfurizing catalyst.
Accompanying drawing explanation
Fig. 1 is XRD diffraction pattern; In Fig. 1,1 is the XRD curve of chromated oxide obtained after the oxidation-desulfurizing catalyst calcining that obtains of test one, the XRD curve of chromated oxide obtained after the 2 oxidation-desulfurizing catalysts calcinings obtained for test two, 3 for butyl titanate calcine after the XRD curve of titanium oxide that obtains;
Fig. 2 is the conversion rate curve of dibenzothiophenes; In Fig. 2,1 is the conversion rate curve of the dibenzothiophenes of chromated oxide obtained after the oxidation-desulfurizing catalyst calcining that obtains of test one, the conversion rate curve of the dibenzothiophenes of chromated oxide obtained after the 2 oxidation-desulfurizing catalysts calcinings obtained for test two, 3 for butyl titanate calcine after the conversion rate curve of the dibenzothiophenes of titanium oxide that obtains;
Fig. 3 is the adsorption curve of the oxidation-desulfurizing catalyst that test one obtains.
Detailed description of the invention
Detailed description of the invention one: present embodiment is that a kind of preparation method of oxidation-desulfurizing catalyst specifically completes according to the following steps:
One, MIL-101 (Cr) precursor solution is prepared: by Cr (NO
3)
39H
2o and terephthalic acid (TPA) join in distilled water, under room temperature and ultrasonic power be ultrasonic disperse 30min ~ 60min under the condition of 160W ~ 200W, obtain the suspension that pH value is 2 ~ 4; By pH value be again 2 ~ 4 suspension join in the polytetrafluoroethyllining lining of autoclave, the autoclave of sealing being put into temperature is heat 16h ~ 18h in the baking oven of 200 DEG C ~ 220 DEG C again, obtains MIL-101 (Cr) precursor solution that pH value is 0.1 ~ 1;
Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of distilled water are 1g:(7mL ~ 16mL);
The quality of the terephthalic acid (TPA) described in step one and the volume ratio of distilled water are 1g:(12mL ~ 80mL);
Two, by pH value be 0.1 ~ 1 MIL-101 (Cr) precursor solution filter, obtain solid matter A; Again by solid matter A dry 6h ~ 8h at temperature is 60 DEG C ~ 80 DEG C, obtain dried solid matter A; Dried solid matter A is joined in absolute ethyl alcohol, then at temperature is 60 DEG C ~ 80 DEG C hydrothermal treatment consists 20h ~ 30h, then to filter, obtain solid matter B; Re-use absolute ethyl alcohol and washing carried out 3 times ~ 4 times to solid matter B, then at temperature is 60 DEG C ~ 80 DEG C dry 1h ~ 2h, obtain dried solid matter B;
The quality of dried solid matter A described in step 2 and the volume ratio of absolute ethyl alcohol are 1g:(40mL ~ 50mL);
Three, dried solid matter B is joined the NH that concentration is 1mol/L ~ 2mol/L
4in F solution, then stir 20h ~ 30h under temperature is 60 DEG C ~ 80 DEG C and mixing speed is 800r/min ~ 1200r/min, then filter, obtain solid matter C; Re-using temperature is that the distilled water of 25 DEG C ~ 30 DEG C carries out washing 3 ~ 4 times to solid matter C, then at temperature is 60 DEG C ~ 80 DEG C dry 6h ~ 8h, obtain dried solid matter C;
The quality of the dried solid matter B described in step 3 and concentration are the NH of 1mol/L ~ 2mol/L
4the volume ratio of F solution is 1g:(30mL ~ 50mL);
Four, by dried solid matter C in temperature be 150 DEG C ~ 200 DEG C and vacuum condition under carry out degassed 10h ~ 12h; Obtain degassed after solid matter C;
Five, titanium source is mixed with solvent, obtain titanium source solution; By obtain in step 4 degassed after solid matter C join in the solution of titanium source, at temperature is 60 DEG C ~ 80 DEG C, heat 10h ~ 20h after mixing, then calcine 2h ~ 6h at temperature be 400 DEG C ~ 600 DEG C, obtain oxidation-desulfurizing catalyst;
In titanium source solution described in step 5, the quality in titanium source and the volume ratio of solvent are 1g:(0.4mL ~ 0.5mL);
In the quality of the solid matter C after degassed described in step 5 and titanium source solution, the mass ratio of titanium atom is 1:(0.1 ~ 0.5).
The advantage of present embodiment: metal-organic framework materials (MOFs) combines with titanium elements by present embodiment, the activated centre of oxidation desulfur reaction not only can be provided, and the special skeleton structure of MOFs can be utilized to obtain porous metal oxide, make titanium elements have good dispersiveness, thus improve the reactivity of 30% ~ 40% oxidation sweetening.
Present embodiment can obtain a kind of preparation method of oxidation-desulfurizing catalyst.
Detailed description of the invention two: present embodiment and detailed description of the invention one difference are: the solvent described in step 5 is absolute methanol, absolute ethyl alcohol or cyclohexane.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 titanium source described in step 5 is tetraethyl titanate, butyl titanate or isopropyl titanate.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 Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of distilled water are 1g:(7mL ~ 12mL).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 terephthalic acid (TPA) described in step one be 1g:(12mL ~ 30mL with the volume ratio of distilled water).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 quality of dried solid matter A described in step 2 and the volume ratio of absolute ethyl alcohol are 1g:(40mL ~ 45mL).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 dried solid matter B described in step 3 and concentration are the NH of 1mol/L ~ 1.5mol/L
4the volume ratio of F solution is 1g:(30mL ~ 40mL).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: be carry out degassed 10h ~ 14h under the condition of 100 DEG C ~ 200 DEG C and vacuum in temperature by dried solid matter C in step 4; Obtain degassed after solid matter C.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 the titanium source solution described in step 5, the quality in titanium source and the volume ratio of solvent are 1g:(0.4mL ~ 0.45mL).Other steps are identical with detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine difference is: mass ratio 1:(0.1 ~ 0.4 of titanium atom in the quality of the solid matter C after degassed described in step 5 and titanium source solution).Other steps are identical with detailed description of the invention one to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of preparation method of oxidation-desulfurizing catalyst, specifically completes according to the following steps:
One, MIL-101 (Cr) precursor solution is prepared: by 6gCr (NO
3)
39H
2o and 2.49g terephthalic acid (TPA) joins in 60mL distilled water, under room temperature and ultrasonic power be ultrasonic disperse 40min under the condition of 180W, obtain the suspension that pH value is 2.48; By pH value be again 2.48 suspension join in the polytetrafluoroethyllining lining of autoclave, then the autoclave of sealing to be put into temperature be heat 18h in the baking oven of 218 DEG C, obtains MIL-101 (Cr) precursor solution that pH value is 0.5;
Two, by pH value be 0.5 MIL-101 (Cr) precursor solution filter, obtain solid matter A; Again by solid matter dry 7h at temperature is 70 DEG C, obtain dried solid matter A; Dried solid matter A is joined in absolute ethyl alcohol, then at temperature is 60 DEG C hydrothermal treatment consists 24h, then to filter, obtain solid matter B; Re-use absolute ethyl alcohol and washing carried out 3 times to solid matter B, then at temperature is 70 DEG C dry 1h, obtain dried solid matter B;
The quality of dried solid matter A described in step 2 and the volume ratio of absolute ethyl alcohol are 1g:40mL;
Three, dried solid matter B is joined the NH that concentration is 1mol/L
4in F solution, then stir 24h under temperature is 70 DEG C and mixing speed is 1000r/min, then filter, obtain solid matter C; Re-using temperature is that the distilled water of 25 DEG C carries out washing 3 times to solid matter C, then at temperature is 70 DEG C dry 6h, obtain dried solid matter C;
The quality of the dried solid matter B described in step 3 and concentration are the NH of 1mol/L
4the volume ratio of F solution is 1g:40mL;
Four, by dried solid matter C in temperature be 150 DEG C and vacuum condition under carry out degassed 12h; Obtain degassed after solid matter C;
Five, butyl titanate is mixed with absolute ethyl alcohol, obtain titanium source solution; By obtain in 0.3g step 4 degassed after solid matter C join in the solution of titanium source, at temperature is 60 DEG C, heat 12h after mixing, then calcine 5h at temperature be 550 DEG C, obtain oxidation-desulfurizing catalyst;
In titanium source solution described in step 5, the quality of butyl titanate and the volume ratio of absolute ethyl alcohol are 1g:0.4mL;
In the quality of the solid matter C after degassed described in step 5 and titanium source solution, the mass ratio of titanium atom is 1:0.1.
Test two: a kind of preparation method of oxidation-desulfurizing catalyst, specifically completes according to the following steps:
One, MIL-101 (Cr) precursor solution is prepared: by 6gCr (NO
3)
39H
2o and 2.49g terephthalic acid (TPA) joins in 60mL distilled water, under room temperature and ultrasonic power be ultrasonic disperse 40min under the condition of 180W, obtain the suspension that pH value is 2.48; By pH value be again 2.48 suspension join in the polytetrafluoroethyllining lining of autoclave, then the autoclave of sealing to be put into temperature be heat 18h in the baking oven of 218 DEG C, obtains MIL-101 (Cr) precursor solution that pH value is 0.5;
Two, by pH value be 0.5 MIL-101 (Cr) precursor solution filter, obtain solid matter A; Again by solid matter dry 7h at temperature is 70 DEG C, obtain dried solid matter A; Dried solid matter A is joined in absolute ethyl alcohol, then at temperature is 60 DEG C hydrothermal treatment consists 24h, then to filter, obtain solid matter B; Re-use absolute ethyl alcohol and washing carried out 3 times to solid matter B, then at temperature is 70 DEG C dry 1h, obtain dried solid matter B;
The quality of dried solid matter A described in step 2 and the volume ratio of absolute ethyl alcohol are 1g:40mL;
Three, dried solid matter B is joined the NH that concentration is 1mol/L
4in F solution, then stir 24h under temperature is 70 DEG C and mixing speed is 1000r/min, then filter, obtain solid matter C; Re-using temperature is that the distilled water of 25 DEG C carries out washing 3 times to solid matter C, then at temperature is 70 DEG C dry 6h, obtain dried solid matter C;
The quality of the dried solid matter B described in step 3 and concentration are the NH of 1mol/L
4the volume ratio of F solution is 1g:40mL;
Four, by dried solid matter C in temperature be 150 DEG C and vacuum condition under carry out degassed 12h; Obtain degassed after solid matter C;
Five, butyl titanate is mixed with absolute ethyl alcohol, obtain titanium source solution; By obtain in 0.3g step 4 degassed after solid matter C join in the solution of titanium source, at temperature is 60 DEG C, heat 12h after mixing, then calcine 5h at temperature be 550 DEG C, obtain oxidation-desulfurizing catalyst;
In titanium source solution described in step 5, the quality of butyl titanate and the volume ratio of absolute ethyl alcohol are 1g:0.4mL;
In the quality of the solid matter C after degassed described in step 5 and titanium source solution, the mass ratio of titanium atom is 1:0.5.
The oxidation-desulfurizing catalyst that 0.5g test one obtains is warming up to 550 DEG C, and calcines 5h under the condition of in air atmosphere with 550 DEG C, obtain chromated oxide, use X-ray diffractometer to test titanium oxide, as shown in 1 curve in Fig. 1;
The oxidation-desulfurizing catalyst that 0.5g test two obtains is warming up to 550 DEG C, and calcines 5h under the condition of in air atmosphere with 550 DEG C, obtain chromated oxide, use X-ray diffractometer to test titanium oxide, as shown in 2 curves in Fig. 1;
0.5g butyl titanate is warming up to 550 DEG C, and calcines 5h under the condition of in air atmosphere with 550 DEG C, obtain titanium oxide, use X-ray diffractometer to test titanium oxide, as shown in 3 curves in Fig. 1.
Fig. 1 is XRD diffraction pattern; In Fig. 1,1 is the XRD curve of chromated oxide obtained after the oxidation-desulfurizing catalyst calcining that obtains of test one, the XRD curve of chromated oxide obtained after the 2 oxidation-desulfurizing catalysts calcinings obtained for test two, 3 for butyl titanate calcine after the XRD curve of titanium oxide that obtains; As can be seen from Figure 1, the oxidation-desulfurizing catalyst that test one and test two obtain is the alloy of chrome green and titanium dioxide, the titanium amount of the oxidation-desulfurizing catalyst load that test one and test two obtain increases, and thing phase composition is constant, and just the peak intensity of titanium dioxide increases.
Fig. 2 is the conversion rate curve of dibenzothiophenes; In Fig. 2,1 is the conversion rate curve of the dibenzothiophenes of chromated oxide obtained after the oxidation-desulfurizing catalyst calcining that obtains of test one, the conversion rate curve of the dibenzothiophenes of chromated oxide obtained after the 2 oxidation-desulfurizing catalysts calcinings obtained for test two, 3 for butyl titanate calcine after the conversion rate curve of the dibenzothiophenes of titanium oxide that obtains; Conversion ratio is the ratio being recorded peak area and the initial peak area of the front dibenzothiophenes of reaction putting reacted dibenzothiophenes sometime by gas-chromatography.As can be seen from Figure 2, when 60min, the conversion ratio of the dibenzothiophenes of the chromated oxide obtained after the oxidation-desulfurizing catalyst calcining that test one obtains is 40%, and the conversion ratio of the dibenzothiophenes of the titanium oxide obtained after butyl titanate calcining during 60min is 8%, and the conversion ratio of the dibenzothiophenes of the chromated oxide obtained after testing the two oxidation-desulfurizing catalyst calcinings obtained during 60min is 80%; As can be seen here, the oxidation-desulfurizing catalysts that test one and test two obtain substantially increase the reactivity of oxidation sweetening.
Fig. 3 is the adsorption curve of the oxidation-desulfurizing catalyst that test one obtains; As can be seen from Figure 3, test an oxidation-desulfurizing catalyst obtained and there is meso-hole structure.
Claims (10)
1. a preparation method for oxidation-desulfurizing catalyst, is characterized in that what a kind of preparation method of oxidation-desulfurizing catalyst specifically completed according to the following steps:
One, MIL-101 (Cr) precursor solution is prepared: by Cr (NO
3)
39H
2o and terephthalic acid (TPA) join in distilled water, under room temperature and ultrasonic power be ultrasonic disperse 30min ~ 60min under the condition of 160W ~ 200W, obtain the suspension that pH value is 2 ~ 4; By pH value be again 2 ~ 4 suspension join in the polytetrafluoroethyllining lining of autoclave, the autoclave of sealing being put into temperature is heat 16h ~ 18h in the baking oven of 200 DEG C ~ 220 DEG C again, obtains MIL-101 (Cr) precursor solution that pH value is 0.1 ~ 1;
Cr (NO described in step one
3)
39H
2the quality of O and the volume ratio of distilled water are 1g:(7mL ~ 16mL);
The quality of the terephthalic acid (TPA) described in step one and the volume ratio of distilled water are 1g:(12mL ~ 80mL);
Two, by pH value be 0.1 ~ 1 MIL-101 (Cr) precursor solution filter, obtain solid matter A; Again by solid matter A dry 6h ~ 8h at temperature is 60 DEG C ~ 80 DEG C, obtain dried solid matter A; Dried solid matter A is joined in absolute ethyl alcohol, then at temperature is 60 DEG C ~ 80 DEG C hydrothermal treatment consists 20h ~ 30h, then to filter, obtain solid matter B; Re-use absolute ethyl alcohol and washing carried out 3 times ~ 4 times to solid matter B, then at temperature is 60 DEG C ~ 80 DEG C dry 1h ~ 2h, obtain dried solid matter B;
The quality of dried solid matter A described in step 2 and the volume ratio of absolute ethyl alcohol are 1g:(40mL ~ 50mL);
Three, dried solid matter B is joined the NH that concentration is 1mol/L ~ 2mol/L
4in F solution, then stir 20h ~ 30h under temperature is 60 DEG C ~ 80 DEG C and mixing speed is 800r/min ~ 1200r/min, then filter, obtain solid matter C; Re-using temperature is that the distilled water of 25 DEG C ~ 30 DEG C carries out washing 3 ~ 4 times to solid matter C, then at temperature is 60 DEG C ~ 80 DEG C dry 6h ~ 8h, obtain dried solid matter C;
The quality of the dried solid matter B described in step 3 and concentration are the NH of 1mol/L ~ 2mol/L
4the volume ratio of F solution is 1g:(30mL ~ 50mL);
Four, by dried solid matter C in temperature be 150 DEG C ~ 200 DEG C and vacuum condition under carry out degassed 10h ~ 12h; Obtain degassed after solid matter C;
Five, titanium source is mixed with solvent, obtain titanium source solution; By obtain in step 4 degassed after solid matter C join in the solution of titanium source, at temperature is 60 DEG C ~ 80 DEG C, heat 10h ~ 20h after mixing, then calcine 2h ~ 6h at temperature be 400 DEG C ~ 600 DEG C, obtain oxidation-desulfurizing catalyst;
In titanium source solution described in step 5, the quality in titanium source and the volume ratio of solvent are 1g:(0.4mL ~ 0.5mL);
In the quality of the solid matter C after degassed described in step 5 and titanium source solution, the mass ratio of titanium atom is 1:(0.1 ~ 0.5).
2. the preparation method of a kind of oxidation-desulfurizing catalyst according to claim 1, is characterized in that the solvent described in step 5 is absolute methanol, absolute ethyl alcohol or cyclohexane.
3. the preparation method of a kind of oxidation-desulfurizing catalyst according to claim 1, is characterized in that the titanium source described in step 5 is tetraethyl titanate, butyl titanate or isopropyl titanate.
4. the preparation method of a kind of oxidation-desulfurizing catalyst 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 distilled water are 1g:(7mL ~ 12mL).
5. the preparation method of a kind of oxidation-desulfurizing catalyst according to claim 1, the quality that it is characterized in that the terephthalic acid (TPA) described in step one be 1g:(12mL ~ 30mL with the volume ratio of distilled water).
6. the preparation method of a kind of oxidation-desulfurizing catalyst according to claim 1, is characterized in that the quality of dried solid matter A described in step 2 and the volume ratio of absolute ethyl alcohol are 1g:(40mL ~ 45mL).
7. the preparation method of a kind of oxidation-desulfurizing catalyst according to claim 1, is characterized in that the quality of the dried solid matter B described in step 3 and concentration are the NH of 1mol/L ~ 1.5mol/L
4volume ratio 1g:(30mL ~ the 40mL of F solution).
8. the preparation method of a kind of oxidation-desulfurizing catalyst according to claim 1, it is characterized in that in step 4 by dried solid matter C in temperature be 100 DEG C ~ 200 DEG C and vacuum condition under carry out degassed 10h ~ 14h; Obtain degassed after solid matter C.
9. the preparation method of a kind of oxidation-desulfurizing catalyst according to claim 1, is characterized in that in the titanium source solution described in step 5, the quality in titanium source and the volume ratio of solvent are 1g:(0.4mL ~ 0.45mL).
10. the preparation method of a kind of oxidation-desulfurizing catalyst according to claim 1, mass ratio 1:(0.1 ~ 0.4 of titanium atom in the quality of the solid matter C after to it is characterized in that described in step 5 degassed and titanium source solution).
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| CN104722338A (en) * | 2015-04-02 | 2015-06-24 | 哈尔滨工业大学 | Preparation method of titanium modified MIL-101(Cr) catalyst |
| CN104741151A (en) * | 2015-04-02 | 2015-07-01 | 哈尔滨工业大学 | Preparation method and application of carbon-doped nanometer compound metal oxide |
| CN105038840A (en) * | 2015-09-09 | 2015-11-11 | 哈尔滨工业大学 | Method for removing thiophenic compounds in oil through homogeneous catalytic oxidation |
| CN105289732A (en) * | 2015-10-22 | 2016-02-03 | 大连理工大学 | MOF supported metal peroxide catalyst |
| CN106669844A (en) * | 2016-12-06 | 2017-05-17 | 北京林业大学 | Synthesis method and application of core-shell-structure oxidative desulfurization catalyst |
| CN107362830A (en) * | 2017-06-27 | 2017-11-21 | 哈尔滨理工大学 | A kind of preparation method of the CdS-loaded hydrogen production photocatalyst of MIL 101 (Cr) |
| CN115433606A (en) * | 2022-10-10 | 2022-12-06 | 深圳职业技术学院 | Application of ammonium vanadyl sulfate as air oxidation desulfurization catalyst |
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| CN105038840A (en) * | 2015-09-09 | 2015-11-11 | 哈尔滨工业大学 | Method for removing thiophenic compounds in oil through homogeneous catalytic oxidation |
| CN105289732A (en) * | 2015-10-22 | 2016-02-03 | 大连理工大学 | MOF supported metal peroxide catalyst |
| CN105289732B (en) * | 2015-10-22 | 2019-04-09 | 大连理工大学 | The immobilized metal peroxides catalyst of MOF |
| CN106669844A (en) * | 2016-12-06 | 2017-05-17 | 北京林业大学 | Synthesis method and application of core-shell-structure oxidative desulfurization catalyst |
| CN107362830A (en) * | 2017-06-27 | 2017-11-21 | 哈尔滨理工大学 | A kind of preparation method of the CdS-loaded hydrogen production photocatalyst of MIL 101 (Cr) |
| CN107362830B (en) * | 2017-06-27 | 2020-01-10 | 哈尔滨理工大学 | Preparation method of MIL-101(Cr) loaded CdS hydrogen production photocatalyst |
| CN115433606A (en) * | 2022-10-10 | 2022-12-06 | 深圳职业技术学院 | Application of ammonium vanadyl sulfate as air oxidation desulfurization catalyst |
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