CN103752276A - Cuprous modified metal organic skeleton adsorbent, preparation method and application - Google Patents
Cuprous modified metal organic skeleton adsorbent, preparation method and application Download PDFInfo
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- CN103752276A CN103752276A CN201410012066.2A CN201410012066A CN103752276A CN 103752276 A CN103752276 A CN 103752276A CN 201410012066 A CN201410012066 A CN 201410012066A CN 103752276 A CN103752276 A CN 103752276A
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Abstract
The invention discloses cuprous modified metal organic skeleton absorbent, a preparation method and application, belonging to the technical field of fuel oil processing. The absorbent can effectively adsorb sulfide in gasoline. The cuprous modified metal organic skeleton absorbent adopts a metal organic skeleton as a carrier, a cupric precursor is reduced by adopting a reducing agent through a vapor induction reduction method to prepare the metal organic skeleton adsorbent which is loaded with monovalent copper, and the cuprous content is 0.1 to 1mmol/g.
Description
Technical field
The present invention relates to a kind of adsorbent, preparation method and application, relate in particular a kind of monovalence copper modified metal organic backbone adsorbent, preparation method and application thereof, belong to fuel oil processing technique field.
Background technology
The gasoline of China approximately 80% is from catalytically cracked gasoline, and sulphur in catalytically cracked gasoline mainly exists with thiophene and derivatives form.At present, the Main Means that reduces sulfur content in fuel oil is hydrofinishing, but not only technological equipment investment is large for the method, and operating cost is high, and can reduce the octane number of gasoline.Because adsorption technology equipment investment cost is low, energy consumption is low, be therefore considered to the very promising method of one, and the key of desulfurization is easily preparation and the good adsorbent of absorption property of exploitation.
Because metal-organic framework materials is easily prepared, monovalence copper cost is low, mode of loading is more and cupric presoma kind is many, and the adsorbent of preparation monovalence copper modification becomes the focus of research.But at present in technology, cupprous on adsorbent obtains general needs and first cupric salt heat treatment is converted into cupric oxide, then passes through high temperature autoreduction (>700 ℃) and obtains (Tian, W.-H.; Sun, L.-B.; Song, X.-L.; Liu, X.-Q.; Yin, Y.; He, G.-S.Langmuir2010,26,17398.), and metallic organic framework can not bear the temperature of cupric high temperature autoreduction, and cupric salt heat treatment is converted into cupric oxide, more further become the step of cuprous oxide more loaded down with trivial details copper oxide reduction.
Summary of the invention
The present invention solves prior art and is inadequate, and a kind of monovalence copper modified metal organic backbone adsorbent is provided, and this adsorbent can carry out adsorbing and removing to the sulfide in gasoline effectively.
Another object of the present invention is to provide the preparation method of the metallic organic framework adsorbent of this monovalence copper modification, will be on metallic organic framework supported copper source, directly cupric is converted into monovalence copper at low temperatures, realizes a step preparation of the metallic organic framework adsorbent of monovalence copper modification.
The application of the metallic organic framework adsorbent that a further object of the present invention is to provide this monovalence copper modification in gasoline desulfur and utilize this adsorbent to carry out the method for gasoline desulfur, provides a kind of for removing the metallic organic framework adsorbent of monovalence copper modification of gasoline thiophene-type sulfide.
Of the present invention being achieved through the following technical solutions:
The metallic organic framework adsorbent of monovalence copper of the present invention modification, it is take metallic organic framework as carrier, utilize reducing agent to adopt steam induction reducing process reduction cupric presoma, make the cupprous metallic organic framework adsorbent of load, wherein monovalence copper content is 0.1～1mmol/g.
The preparation method of the metallic organic framework adsorbent of the above-mentioned monovalence copper modification of the present invention, it comprises the following steps:
Cupric salt is carried on metallic organic framework by infusion process, the sample filtering of gained, after oven dry, be placed in reactor, reducing agent separates with open container, guarantee directly not contact with sample, be heated under 150～250 ℃ of conditions and carry out reduction reaction, reducing agent volatilization produces steam, diffuse on sample and react with the cupric in sample, thereby make the cupprous metallic organic framework adsorbent of load, wherein cupric salt solution concentration is 25～100mg/mL, the mass ratio of cupric salt and carrier metal organic backbone is 0.05～0.2, cupric salt is 0.001～0.008 with the ratio of the mole of reducing agent, the reduction reaction time is 5～10h.
The preparation method of the metallic organic framework adsorbent of monovalence copper of the present invention modification, its further technical scheme is that described cupric salt is the one in Schweinfurt green, copper sulphate, copper nitrate and copper chloride.
The preparation method of the metallic organic framework adsorbent of monovalence copper of the present invention modification, its further technical scheme can also be that described carrier metal organic backbone is to react the one in metallic organic framework MIL-53, MIL-47, HKUST-1, MIL-101, ZIF-8, MOF-5 or the MOF-177 making by slaine and organic ligand.
The preparation method of the metallic organic framework adsorbent of monovalence copper of the present invention modification, its further technical scheme can also be that described reducing agent is acetaldehyde, hydrazine hydrate, formic acid, methyl alcohol, ethanol, formaldehyde and N, the one in N '-dimethyl formamide.
The metallic organic framework adsorbent of the above-mentioned monovalence copper modification of the present invention can applying in gasoline desulfur.
The application of the metallic organic framework adsorbent of monovalence copper of the present invention modification in gasoline desulfur, its step is that the metallic organic framework adsorbent of monovalence copper modification is contacted with sour gasoline, utilizes absorption method to realize the desulfurization of gasoline.
The application of the metallic organic framework adsorbent of monovalence copper of the present invention modification in gasoline desulfur, its further technical scheme is that the condition that the metallic organic framework adsorbent of described monovalence copper modification contacts with sour gasoline is: temperature is 20～50 ℃, and pressure is 0.1～0.5MPa.
The application of the metallic organic framework adsorbent of monovalence copper of the present invention modification in gasoline desulfur, its further technical scheme can also be that described sour gasoline is thiophene-type sulfide gasoline, wherein said thiophene-type sulfide is one or more in thiophene, benzothiophene or 4,6-dimethyl, two Thianaphthenes
Compared with prior art the present invention has following beneficial effect:
The present invention utilizes the redox reaction of cupric salt on metallic organic framework and reducing agent steam at a lower temperature, and a step is prepared the metallic organic framework adsorbent of a kind of monovalence copper modification, and effectively for removing the thiophene sulphur of gasoline.Preparation method provided by the invention is lower than existing method reduction temperature, be easy to control, step is simple, and on gained sample, the percent reduction of active component cuprous oxide is high.
The specific embodiment
The following examples will be further described the present invention, but content of the present invention is not limited to this completely.
Embodiment 1
The preparation of adsorbent: take 0.5g copper sulphate and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier MIL-53 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.11mmol/g.
Embodiment 2
The preparation of adsorbent: take 0.5g Schweinfurt green and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier MIL-53 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.12mmol/g.
Embodiment 3
The preparation of adsorbent: take 0.5g copper nitrate and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier MIL-53 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.12mmol/g.
Embodiment 4
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier MIL-53 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.13mmol/g.
Embodiment 5
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier HKUST-1 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.13mmol/g.
Embodiment 6
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier MOF-5 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.13mmol/g.
Embodiment 7
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier MOF-177 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.13mmol/g.
Embodiment 8
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier MIL-47 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.13mmol/g.
Embodiment 9
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formic acid isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 500ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 10
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier MIL-101 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL methyl alcohol isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 11
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL formaldehyde isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.05mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 12
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL ethanol isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 13
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and the placement of 2mL acetaldehyde isolation, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIAN CP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 14
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL hydrazine hydrate isolation placement, be placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 15
The preparation of adsorbent: take 0.5g copper chloride and be dissolved in 10mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 0.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.2g is placed in reactor and 2mL N, one isolation in N '-dimethyl formamide is placed, and is placed in 10h in 150 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.1g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 16
The preparation of adsorbent: take 1.5g copper chloride and be dissolved in 20mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 1g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.5g is placed in reactor and 2mL N, one isolation in N '-dimethyl formamide is placed, and is placed in 5h in 250 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.2g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 17
The preparation of adsorbent: take 1.5g copper sulphate and be dissolved in 20mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 1g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.5g is placed in reactor and 1mL N, one isolation in N '-dimethyl formamide is placed, and is placed in 5h in 250 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.2g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 18
The preparation of adsorbent: take 1.5g copper sulphate and be dissolved in 20mL deionized water, treat that it fully dissolves, the carrier ZIF-8 that takes 1g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.5g is placed in reactor and 1mL N, one isolation in N '-dimethyl formamide is placed, and is placed in 5h in 200 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.2g and be placed in glass column, with the speed of 3mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 19
The preparation of adsorbent: take 1.5g copper sulphate and be dissolved in 20mL deionized water, treat that it fully dissolves, the carrier MIL-101 that takes 1g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.5g is placed in reactor and 1mL N, one isolation in N '-dimethyl formamide is placed, and is placed in 5h in 200 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.2g and be placed in glass column, with the speed of 2mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Embodiment 20
The preparation of adsorbent: take 1.5g copper nitrate and be dissolved in 20mL deionized water, treat that it fully dissolves, the carrier MIL-101 that takes 1.5g is placed in above-mentioned solution, filtering drying after stirring certain hour, getting the above-mentioned gained sample of 0.5g is placed in reactor and 1mL N, one isolation in N '-dimethyl formamide is placed, and is placed in 5h in 200 ℃ of baking ovens, can obtain after cooling the metallic organic framework adsorbent of load cuprous oxide.
Desulfurization: adopt dynamic adsorption method to measure the desulfurization performance of adsorbent.Get above-mentioned adsorbent 0.2g and be placed in glass column, with the speed of 2mL/h, pass into the mould oil of sulfur content 800ppm, absorption at normal temperatures, utilize Valley peace chromatogram VARIANCP-3800 to adsorb the analysis of rear model content of sulfur in gasoline, the capacity that penetrates of adsorbent is 0.1mmol/g, and saturated adsorption capacity is 0.15mmol/g.
Claims (9)
1. the metallic organic framework adsorbent of monovalence copper modification, it is characterized in that take metallic organic framework as carrier, utilize reducing agent to adopt steam induction reducing process reduction cupric presoma, make the cupprous metallic organic framework adsorbent of load, wherein monovalence copper content is 0.1～1mmol/g.
2. the preparation method of the metallic organic framework adsorbent of monovalence copper according to claim 1 modification, is characterized in that comprising the following steps:
Cupric salt is carried on metallic organic framework by infusion process, the sample filtering of gained, after oven dry, be placed in reactor, reducing agent separates with open container, guarantee directly not contact with sample, be heated under 150～250 ℃ of conditions and carry out reduction reaction, reducing agent volatilization produces steam, diffuse on sample and react with the cupric in sample, thereby make the cupprous metallic organic framework adsorbent of load, wherein cupric salt solution concentration is 25～100mg/mL, the mass ratio of cupric salt and carrier metal organic backbone is 0.05～0.2, cupric salt is 0.001～0.008 with the ratio of the mole of reducing agent, the reduction reaction time is 5～10h.
3. the preparation method of the metallic organic framework adsorbent of monovalence copper according to claim 2 modification, is characterized in that described cupric salt is the one in Schweinfurt green, copper sulphate, copper nitrate and copper chloride.
4. the preparation method of the metallic organic framework adsorbent of monovalence copper according to claim 2 modification, is characterized in that described carrier metal organic backbone is to react the one in metallic organic framework MIL-53, MIL-47, HKUST-1, MIL-101, ZIF-8, MOF-5 or the MOF-177 making by slaine and organic ligand.
5. the preparation method of the metallic organic framework adsorbent of monovalence copper according to claim 2 modification, is characterized in that described reducing agent is acetaldehyde, hydrazine hydrate, formic acid, methyl alcohol, ethanol, formaldehyde and N, the one in N '-dimethyl formamide.
6. the application of the metallic organic framework adsorbent of a monovalence copper as claimed in claim 1 modification in gasoline desulfur.
7. the application of the metallic organic framework adsorbent of monovalence copper according to claim 6 modification in gasoline desulfur, it is characterized in that step is that the metallic organic framework adsorbent of monovalence copper modification is contacted with sour gasoline, utilizes absorption method to realize the desulfurization of gasoline.
8. the application of the metallic organic framework adsorbent of monovalence copper according to claim 7 modification in gasoline desulfur, the condition that the metallic organic framework adsorbent of the monovalence copper modification described in it is characterized in that contacts with sour gasoline is: temperature is 20～50 ℃, and pressure is 0.1～0.5MPa.
9. the application of the metallic organic framework adsorbent of monovalence copper according to claim 7 modification in gasoline desulfur, is characterized in that described sour gasoline is thiophene-type sulfide gasoline.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886244A (en) * | 2012-05-18 | 2013-01-23 | 天津工业大学 | Metal-organic framework hybrid membrane for desulfuration, and manufacturing method thereof |
| CN103007874A (en) * | 2012-12-13 | 2013-04-03 | 南京工业大学 | Supported cuprous oxide adsorbent as well as preparation method, application and regeneration method thereof |
| CN103331139A (en) * | 2013-06-20 | 2013-10-02 | 南京工业大学 | Preparation method of copper-containing load-type adsorbent |
-
2014
- 2014-01-10 CN CN201410012066.2A patent/CN103752276A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886244A (en) * | 2012-05-18 | 2013-01-23 | 天津工业大学 | Metal-organic framework hybrid membrane for desulfuration, and manufacturing method thereof |
| CN103007874A (en) * | 2012-12-13 | 2013-04-03 | 南京工业大学 | Supported cuprous oxide adsorbent as well as preparation method, application and regeneration method thereof |
| CN103331139A (en) * | 2013-06-20 | 2013-10-02 | 南京工业大学 | Preparation method of copper-containing load-type adsorbent |
Non-Patent Citations (1)
| Title |
|---|
| NAZMUL ABEDIN KHAN等: "Low-temperature loading of Cu+ species over porous metal-organic frameworks (MOFs) and adsorptive desulfurization with Cu+-loaded MOFs", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
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