CN102513102A - Preparation method and application of titanium dioxide loaded ruthenium catalyst - Google Patents
Preparation method and application of titanium dioxide loaded ruthenium catalyst Download PDFInfo
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- CN102513102A CN102513102A CN2011103739581A CN201110373958A CN102513102A CN 102513102 A CN102513102 A CN 102513102A CN 2011103739581 A CN2011103739581 A CN 2011103739581A CN 201110373958 A CN201110373958 A CN 201110373958A CN 102513102 A CN102513102 A CN 102513102A
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- carbon dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 35
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 238000003760 magnetic stirring Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 claims 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 21
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NZIGZHDIUCTKQH-UHFFFAOYSA-N Cl[Ru+2].[NH4+] Chemical compound Cl[Ru+2].[NH4+] NZIGZHDIUCTKQH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a low-load-capacity and high-activity load type ruthenium catalyst using titanium dioxide as a carrier. According to the invention, the titanium dioxide is used as the carrier, an ageing solution is illuminated by using ultraviolet rays in a precipitation and deposition ageing process, thus interaction of a ruthenium precursor and the titanium dioxide is enhanced, the dispersion degree of the precursor is improved, and further the high-dispersion titanium dioxide loaded ruthenium catalyst is obtained. The preparation method has the advantages of simple equipment and process, high yield, and convenience for industrialized production; and the prepared ruthenium catalyst has the advantages of small ruthenium granularity and good reproducibility. The ruthenium catalyst is applied to a process for synthesizing methane by carbon dioxide through hydrogenation, and has high reactant transformation rate, high selectivity and good stability.
Description
Technical field
The invention belongs to catalyst preparation technical field, being specifically related to a kind of is the high activity loading type ruthenium catalyst and preparation method thereof of carrier with titanium dioxide, and has studied its catalysis hydrogenation of carbon dioxide methanation reaction.
Background technology
Expanding economy has caused carbon dioxide to discharge in a large number, and this has brought problems for the global environment weather, therefore how to realize carbon dioxide fixation and efficient the utilization, is a human current difficult task that faces.The carbon dioxide catalytic production of methane is converted into useful fuel methane to cheap carbon dioxide, effectively utilizes as a kind of realization carbon dioxide to promote the carbon cycle method, receives in recent years widely and paying close attention to.But because high thermodynamic stability of carbon dioxide and higher oxidation state, the activation of carbon dioxide and methanation reaction usually need higher temperature 300-400 ℃.High reaction temperature needs higher energy consumption on the one hand, also causes the sintering inactivation of catalyst on the other hand easily.Therefore catalyst system reasonable in design reduces the carbon dioxide methanation reaction temperature, has important practical significance.
Ruthenium-based catalyst has best low-temperature carbon dioxide methanation activity and selectivity.The decentralization of metal Ru has big influence to the carbon dioxide methanation activity; Carrier also has remarkable influence to the carbon dioxide methanation activity in addition.Usually the carrier titanium dioxide of reducibility is than unreducible carrier silica, and alundum (Al etc. show better methanation activity.The preparation method commonly used of carbon dioxide methanation supported ruthenium catalyst is an equi-volume impregnating at present.The advantage of this method is that apparatus and process is simple, productive rate is high, is convenient to suitability for industrialized production; Shortcoming is that the ruthenium grain diameter of preparation is big, skewness.Also have the researcher to report recently to use the method for physical sputtering to prepare the ruthenium-based catalyst of high dispersive, but that this method requires is high to apparatus and process, cost is expensive, is difficult to realize commercial Application.
To carbon dioxide methanation Effect on Performance reason, it is generally acknowledged that metal dispersity is high about metal dispersity and carrier, the metallic atom that is considered to the surface in catalytic activity site significantly increases, and then increases the catalytic performance of catalyst; In addition about the effect of carrier to catalytic reaction; The effect of discovering carrier not only shows active component is disperseed; Certain electronics possibly take place between prior carrier and the active component or gone up for how much interact; Even might metal and carrier formed new avtive spot at the interface, reaction has remarkable influence to the catalysis carbon dioxide methanation for this.
Summary of the invention
The purpose of this invention is to provide a kind of is the highly active load ruthenium catalyst of low load capacity and preparation method thereof of carrier with titanium dioxide.
The method that the present invention prepares the titanium dichloride load ruthenium catalyst is the improved deposition-sedimentation of ultraviolet ray irradiation: in the suspension of titanium dioxide, add the ruthenium source; Be adjusted to certain pH value; The aging certain hour of ultraviolet lighting then, the drying and roasting reduction promptly gets the titanium dichloride load ruthenium catalyst.
The titanium dichloride load ruthenium catalyst of the present invention's preparation is carrier with the nano titanium oxide, and wherein the active component ruthenium is dispersed in the surface of carrier with the Nano grade even grain size.
Concrete preparation process of the present invention is following: under the 0-100 ℃ of condition, measuring concentration is the ruthenium source aqueous solution 10-200ml of 0.1-10g/L, adds 0.5-10g titanium dioxide, ultrasonic 1-20min, magnetic agitation 5-20min; Working concentration is that the alkali lye of 0.1-2M transfers to the pH value of the suspension that obtains between the 6-12 under the condition of magnetic agitation, then the aging 0.5-10h of the ultraviolet source irradiation of 0-100 ℃ of following 100-800W; With reacted slurries centrifuge washing 3-10 time, take out 200-600 ℃ of roasting 1-10h behind the 60-120 ℃ of dry 5-30h; Use hydrogen volume concentration under 100-600 ℃ of temperature, to reduce 1-10h and obtain the titanium dichloride load ruthenium catalyst as the hydrogen of 0.05-1 and nitrogen mixture body; Putting into vacuum desiccator after the taking-up preserves.
Described ruthenium source is ruthenic chloride, ruthenium hydrochloride ammonium, nitric acid ruthenium or nitrosyl radical nitric acid ruthenium.
Described titanium dioxide is nanometer anatase titanium dioxide, nano rutile-type or nanometer mixed phase titanium dioxide P25.
Described alkali lye is NaOH, potassium hydroxide, ammoniacal liquor or sodium carbonate liquor.
The present invention is prepared the titanium dichloride load ruthenium catalyst be used for catalysis hydrogenation of carbon dioxide methanation reaction.Concrete reaction condition is: reaction temperature 100-500 ℃, the reaction pressure normal pressure is loaded the titanium dichloride load ruthenium catalyst 0.01-5g of above-mentioned preparation, feeds 10-200ml unstripped gas reaction 4-80 hour; Unstripped gas is the gaseous mixture of carbon dioxide and hydrogen, and the volume ratio of carbon dioxide and hydrogen is (1: 1)-(1: 5).
The invention has the advantages that: select that with metal the titanium dioxide of specific interaction to be arranged be carrier for use; In the aging process of deposition-deposition, use UV-irradiation; Strengthen metal Ru precursor and carrier interactions; Improved the decentralization of precursor, effectively stoped sintering, prepared the titanium dichloride load high dispersive ruthenium catalyst of low temperature high activity at follow-up roasting and reduction process ruthenium nano-particle.This method has that apparatus and process is simple, productive rate is high, be convenient to suitability for industrialized production, and the ruthenium granularity of preparation is little, high repeatability and other advantages.With the reaction of this catalyst applications in the hydrogenation of carbon dioxide synthesizing methane, the conversion ratio of 220 ℃ of carbon dioxides is 98.5%, and the selectivity of target product methane is 100%; Reaction temperature is low; Reaction-ure conversion-age is high, and product selectivity is high, and catalyst stability is good.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the titanium dichloride load ruthenium catalyst of embodiment 1 preparation.
The specific embodiment
Below in conjunction with embodiment the present invention is done further description:
Embodiment 1
Under 25 ℃ of conditions, measure 2.0g/L nitric acid ruthenium solution 80ml in the 300ml beaker, add titanium dioxide 5g, ultrasonic 10min, magnetic agitation 20min; Use the pH value to 6 of this suspension of sodium hydroxide solution adjusting of 1M; Under the 250W ultraviolet light, shine 4h under the stirring condition; Reaction rear slurry centrifuge washing 3 times, 110 ℃ of dryings are taken out behind the 10h; 400 ℃ of air roasting 4h, using hydrogen volume concentration is to obtain the titanium dichloride load ruthenium catalyst after 400 ℃ of reduction of hydrogen and nitrogen mixture body 3h of 0.4 lowers the temperature; Taking-up is put into vacuum desiccator and is preserved.
Titanium dioxide is nanometer mixed phase titanium dioxide P25.
The active component ruthenium is dispersed in the surface of carrier titanium dioxide in the titanium dichloride load ruthenium catalyst of preparation with the Nano grade even grain size.
The titanium dichloride load ruthenium catalyst catalysis hydrogenation of carbon dioxide of above-mentioned preparation is generated methane; Reaction condition is: 300 ℃ of reaction temperatures, and the reaction pressure normal pressure is loaded the titanium dichloride load ruthenium catalyst 1g of above-mentioned preparation; Feed the 60ml unstripped gas; Unstripped gas is the gaseous mixture of carbon dioxide and hydrogen, and the volume ratio of carbon dioxide and hydrogen is 1: 4, reacting balance time 4h.
Use Tianjin, island company gas-chromatography to carry out on-line quantitative analysis to product, through test, the reactant carbon dioxide conversion is 90%, and the selectivity of target product methane is 100%.
Embodiment 2
Under 25 ℃ of conditions, measure 2.0g/L nitrosyl radical nitric acid ruthenium solution 80ml, add titanium dioxide 5g, ultrasonic 10min, magnetic agitation 20min; Use the pH value to 9 of this suspension of sodium hydroxide solution adjusting of 1M; Under the 650W ultraviolet light, shine 4h under the stirring condition; Reaction rear slurry centrifuge washing 3 times, 110 ℃ of dryings are taken out behind the 10h; 400 ℃ of air roasting 4h, using hydrogen volume concentration is to obtain the titanium dichloride load ruthenium catalyst after 400 ℃ of reduction of hydrogen and nitrogen mixture body 3h of 0.4 lowers the temperature; Taking-up is put into vacuum desiccator and is preserved.
Titanium dioxide is nanometer mixed phase titanium dioxide P25.
The active component ruthenium is dispersed in the surface of carrier titanium dioxide in the titanium dichloride load ruthenium catalyst of preparation with the Nano grade even grain size.
The titanium dichloride load ruthenium catalyst catalysis hydrogenation of carbon dioxide of above-mentioned preparation is generated methane; Reaction condition is: 400 ℃ of reaction temperatures, and the reaction pressure normal pressure is loaded the titanium dichloride load ruthenium catalyst 1g of above-mentioned preparation; Feed the 180ml unstripped gas; Unstripped gas is the gaseous mixture of carbon dioxide and hydrogen, and the volume ratio of carbon dioxide and hydrogen is 1: 4, reacting balance time 4h.
Use Tianjin, island company gas-chromatography to carry out on-line quantitative analysis to product, through test, the reactant carbon dioxide conversion is 97%, and the selectivity of target product methane is 100%.
Embodiment 3
Under 80 ℃ of conditions, measure 2.0g/L ruthenic chloride solution 80ml, add titanium dioxide 5g, ultrasonic 10min, magnetic agitation 20min; Use the pH value to 9 of this suspension of sodium hydroxide solution adjusting of 1M; Under the 250W ultraviolet light, shine 4h under the stirring condition; Reaction rear slurry centrifuge washing 3 times, 110 ℃ of dryings are taken out behind the 10h; 550 ℃ of air roasting 4h, using hydrogen volume concentration is to obtain the titanium dichloride load ruthenium catalyst after 200 ℃ of reduction of hydrogen and nitrogen mixture body 5h of 0.4 lowers the temperature; Taking-up is put into vacuum desiccator and is preserved.
Titanium dioxide is nanometer mixed phase titanium dioxide P25.
The active component ruthenium is dispersed in the surface of carrier titanium dioxide in the titanium dichloride load ruthenium catalyst of preparation with the Nano grade even grain size.
The titanium dichloride load ruthenium catalyst catalysis hydrogenation of carbon dioxide of above-mentioned preparation is generated methane; Reaction condition is: 220 ℃ of reaction temperatures, and the reaction pressure normal pressure is loaded the titanium dichloride load ruthenium catalyst 1g of above-mentioned preparation; Feed the 100ml unstripped gas; Unstripped gas is the gaseous mixture of carbon dioxide and hydrogen, and the volume ratio of carbon dioxide and hydrogen is 1: 4, reacting balance time 4h.
Use Tianjin, island company gas-chromatography to carry out on-line quantitative analysis to product, through test, the reactant carbon dioxide conversion is 98.5%, and the selectivity of target product methane is 100%.
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103464148A (en) * | 2013-09-29 | 2013-12-25 | 大连瑞克科技有限公司 | Method for preparing synthetic natural gas low-ruthenium methanation catalyst |
| CN104016825A (en) * | 2014-06-05 | 2014-09-03 | 天津大学 | A technology that uses sunlight and photothermal catalysts to directly convert carbon dioxide to produce organic fuels |
| CN105195138A (en) * | 2015-09-17 | 2015-12-30 | 福州大学 | Visible-light response supported-type Ru catalyst |
| JP2017013040A (en) * | 2015-06-30 | 2017-01-19 | コリア インスティチュート オブ エナジー リサーチ | Method for producing a catalyst comprising a ruthenium-containing catalyst layer formed on the surface of a structure |
| CN106861683A (en) * | 2015-12-10 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of Ru bases catalyst and its in CO2Application in methanation |
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| CN108686635A (en) * | 2018-05-09 | 2018-10-23 | 南通龙翔新材料科技股份有限公司 | Titanium dioxide loaded ruthenium catalyst and preparation method thereof |
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