CN102728364A - Mesoporous carbon supported copper-based metal oxide catalyst and its preparation method - Google Patents
Mesoporous carbon supported copper-based metal oxide catalyst and its preparation method Download PDFInfo
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Abstract
The invention provides a mesoporous carbon supported copper-based metal oxide catalyst and its preparation method. In comparison with the prior art, the invention requires no noble metals and toxic metal oxide during the preparation process of the copper-based catalyst and has characteristics of low cost and environmental protection. In addition, the catalyst has high surface area and large aperture, which is benefit for rapid diffusion of reactants and products inside pore canals so as to avoid deep oxidation, coking and carbon formation. The activity of the catalyst provided by the invention is obviously higher than that of an active carbon supported copper-based metal oxide catalyst.
Description
One, technical field
The present invention relates to the catalyst of preparing isobutene through dehydrogenation of iso-butane, what be specifically related to is copper-based catalysts of mesoporous carbon load and preparation method thereof.
Two, background technology
Isobutene is a kind of important Organic Chemicals; Not only can be used for elastomers such as synthetic butyl rubber, isoprene rubber and Oppanol, also can be used for producing simultaneously multiple fine chemicals such as isoprene, methyl methacrylate, the pure and mild methyl tertiary butyl ether(MTBE) of the tert-butyl group.The tradition source of isobutene mainly comes from naphtha steam cracking system ethylene unit and oil plant fluid catalytic cracking of heavy oil device.In recent years, along with modern chemical industry to the growing of isobutene raw materials requirement and harsh day by day to purity requirement, technologies such as preparing isobutene through dehydrogenation of iso-butane, n-butene isomerization preparing isobutene have also appearred successively.Wherein, the isobutene by dehydrogenation of isobutane production has become the third-largest in the world isobutene source.
At present, the preparing isobutene through dehydrogenation of iso-butane industrialized producing technology of having reported carries out under oxygen free condition usually, adopts chromium system or platinum group catalyst.Wherein, adopt the technology of chromium-based catalysts to comprise the Catofin technology of Abb Lummus company, the FBD-4 technology of Snamprogetti company; Adopt the technology of platinum group catalyst to comprise the Oleflex technology of Uop Inc., the Star technology of Philips company and the Linde technology of Linde company.Yet the iso-butane direct dehydrogenation receives thermodynamics equilibrium limit in the above technology, can not obtain higher isobutene yield.
In order to impel the further conversion of iso-butane to isobutene, carbon dioxide has also appearred in reaction atmosphere, adding recently, and realization dehydrogenation and water-gas reverse shift reaction are coupled and improve the report of iso-butane conversion ratio and selective isobutene.For example, people such as Ogonowski to adopt surface area be 21m
2g
-1The V-Mg-O catalyst, be under 600 ℃ the condition, to have compared inert atmosphere He gas and CO in reaction temperature
2The dehydrogenation activity of iso-butane in the atmosphere.The result shows that catalyst has better dehydrogenation activity under the carbon dioxide atmosphere, and the iso-butane conversion ratio can reach 13%, and selective isobutene is higher than 80% (Catalysis Communications, volume was the 132nd ~ 136 page in 2009 11).People such as Shimada adopt activated carbon supported Fe
2O
3Catalyst; The conversion ratio of iso-butane can reach 23% under 600 ℃ of conditions, and selective isobutene is 80%, but this catalyst activity decay is very fast; React after 3 hours the iso-butane conversion ratio and reduce to 13% (Applied Catalysis A:General, volume was the 243rd ~ 250 page in 1998 168).People such as Ding find activated carbon supported Cr
2O
3In carbon dioxide atmosphere, all have higher dehydrogenation of isobutane initial activity with the NiO catalyst, but catalyst all can't overcome decay of activity faster shortcoming (Chinese Chemical Letters, 2008 19 the volume the 1059th ~ 1062 page; Journal of Molecular Catalysis A:Chemical, volume was the 221st ~ 225 page in 2010 315).
CuO is not only one type of important oxidation catalyst, and is the important activity component in the water-gas shift reaction catalyst.The present invention should have the angle in oxidation center and Water gas shift/WGS activated centre simultaneously from carbon dioxide oxidation catalyst for preparing isobutene through dehydrogenation of iso-butane, has prepared highly active copper base supported catalyst.Do not see any pertinent literature report with CuO as yet as the main active component of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane.
Three, summary of the invention
The copper base metal oxide catalyst that the purpose of this invention is to provide a kind of mesoporous carbon load.
Technical scheme of the present invention is following:
A kind of copper base metal oxide catalyst of mesoporous carbon load is characterized in that: in described catalyst, active component CuO counts 2 ~ 20% by the quality percentage composition, and is preferred 5 ~ 20%, and auxiliary agent oxide mass percentage composition counts 0 ~ 3%, and all the other are mesoporous carbon.
Said auxiliary agent oxide is selected from V
2O
5, Li
2O, MgO, K
2O, CaO, Ga
2O
3, ZnO, Al
2O
3, CeO
2Or La
2O
3In at least a, preferred Li
2O or K
2One or both combinations of O, the effect of auxiliary agent can improve life of catalyst.
Two of the object of the invention provides a kind of preparation method of the copper base metal oxide catalyst with the mesoporous carbon load.
A kind of preparation method of copper base metal oxide catalyst of mesoporous carbon load may further comprise the steps::
(1) takes by weighing the solvable inorganic salts of copper, the solvable inorganic salts and the citric acid of auxiliary agent; Be mixed with the aqueous solution of mantoquita; Be that 3.0 ~ 24.0 g/L, the solvable inorganic salt concentration of auxiliary agent are 0 ~ 7.6 g/L by metal atomic mass concentration in elemental copper atom concentration wherein, the solvable inorganic salts mass ratio of citric acid and copper is 0.4 ~ 2.0;
(2) in the above-mentioned aqueous solution, be that 0.016 ~ 0.255 ratio adds mesoporous carbon in copper and mesoporous carbon mass ratio, stirring, oven dry, roasting promptly get the copper base metal oxide catalyst of mesoporous carbon load.
The solvable inorganic salts of copper described in the above-mentioned preparation method and auxiliary agent are selected from acetate, sulfate, nitrate or halide salt, preferred acetate, nitrate or chlorate.
Among the above-mentioned preparation method, described oven dry is 60 ~ 150 ℃ of oven dry.
Among the above-mentioned preparation method, described roasting is through 500 ~ 750 ℃ of roastings 3 ~ 8 hours at inert atmosphere.
Above-mentioned preparation method, the used inert atmosphere of roasting is meant O
2Volumetric concentration is lower than 0.1% high-purity N
2, a kind of in high-purity Ar or the high-purity He gas.
Described carrier mesoporous carbon, BET specific area 1200 ~ 3100 m
2/ g; The most probable aperture is 2 ~ 8 nm; Pore volume is at 1.0 ~ 3.2 ml/g; In porosity be 75 ~ 100%, preferred mesoporous carbon comprises commodity CMK-1 with orderly pore structure, CMK-3, by unordered mesoporous carbon (unordered mesoporous carbon preparation can be with reference to Journal of Materials Chemistry, and volume was 7759 ~ 7764 pages in 2009 the 19th), CNT and the nanometer rods of organic carbon hydrate, metal halide carbonization preparation.
Carbon dioxide oxidation dehydrogenation of isobutane provided by the invention is that catalyst of the present invention is seated in the reactor; The control temperature of reactor is at 550 ~ 650 ℃; Pressure 0.1 ~ 1.0 Mpa; Iso-butane and carbon dioxide mix gas that it is 1:0.5 ~ 1:11 that feeding is preheated to ratio 320 ~ 450 ℃, amount of substance, the overall flow rate of gas be every gram catalyst 1 ~ 8 mark rise/hour.
The present invention finds, in the preparation process, adds citric acid and can promote the CuO species of load to disperse in the mesoporous carbon surface height, improves catalytic activity.
The carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane copper-based catalysts that is used for of mesoporous carbon load provided by the invention prepares process and does not use noble metal and toxic metals oxide; Have characteristics with low cost and environment amenable; And catalyst has higher surface area and big aperture; Be beneficial to reactant and the product rapid diffusion in the duct, avoided the generation of deep oxidation, coking and carbon distribution, catalyst activity is apparently higher than activated carbon supported copper base metal oxide catalyst.
A kind of carbon dioxide oxidation catalyst for preparing isobutene through dehydrogenation of iso-butane provided by the invention, the conversion ratio of iso-butane can reach 16 ~ 70%, and selective isobutene can reach 70 ~ 95%, has the favorable industrial application prospect.
The specific embodiment
Embodiment 1:
42.4 g copper nitrates and 44.6 g citric acids are dissolved in the 600 mL water, are made into the mixed solution of copper nitrate and citric acid, in above-mentioned solution, adding surface area is 1320 m
2g
-1, the most probable aperture is CMK-3 mesoporous carbon 158.8 g of 4.3 nm; In 70 ℃ of waters bath with thermostatic control, stirred 10 minutes, through 150 ℃ of oven dry, roasting is 5 hours under 680 ℃ of blanket of nitrogen; Promptly get the CuO composite catalyst of mesoporous carbon load, measuring wherein, CuO quality percentage composition is 9.9%.The CuO composite catalyst of prepared mesoporous carbon load is packed in the fixed bed reactors, feed be preheated to 340 ℃ amount of substance than being the iso-butane of 1:6 and carbon dioxide gas mixture, be 5 L/ (g in 0.1Mpa, air speed
CatH) and under the condition of 630 ℃ of reaction temperatures, reacting the conversion ratio that records iso-butane after 1 hour is 58%, and selective isobutene is 88.6%, reacts after 3 hours, and recording the iso-butane conversion ratio is 51%, and selective isobutene is 89.2%.
Comparative Examples 1:
42.4 g copper nitrates and 44.6 g citric acids are dissolved in the 600 mL water, are made into the mixed solution of copper nitrate and citric acid, in above-mentioned solution, adding surface area is 1420 m
2g
-1, the most probable aperture is at activated carbon 158.8 g of 0.8 nm; In 70 ℃ of waters bath with thermostatic control, stirred 10 minutes, through 150 ℃ of oven dry, roasting is 5 hours under 680 ℃ of blanket of nitrogen; Promptly get activated carbon supported CuO composite catalyst, measuring wherein, CuO quality percentage composition is 10.1%.Prepared activated carbon loaded CuO composite catalyst is packed in the fixed bed reactors, feed be preheated to 340 ℃ amount of substance than being the iso-butane of 1:6 and carbon dioxide gas mixture, be 5 L/ (g in 0.1Mpa, air speed
CatH) and under the condition of 630 ℃ of reaction temperatures, reacting the conversion ratio that records iso-butane after 1 hour is 33%, and selective isobutene is 89.1% in the product.
Embodiment 2:
10.0 g Schweinfurt greens and 20.1 g citric acids are dissolved in the 1150 mL water, are made into the mixed solution of Schweinfurt green and citric acid, in above-mentioned solution, adding surface area is 1230 m
2g
-1, the most probable aperture is that unordered mesoporous carbon 214.5 g of 6.0 nm are (with reference to Journal of Materials Chemistry; 7764 pages of preparations of 2009 the 19th volume 7759 –); In 70 ℃ of waters bath with thermostatic control, stirred 10 minutes, through 120 ℃ of oven dry, roasting is 5 hours under 680 ℃ of blanket of nitrogen; Promptly get the CuO composite catalyst of mesoporous carbon load, measuring wherein, CuO quality percentage composition is 2.0%.The CuO composite catalyst of prepared mesoporous carbon load is packed in the fixed bed reactors, feed be preheated to 300 ℃ amount of substance than being the iso-butane of 1:4 and carbon dioxide gas mixture, be 4 L/ (g in 0.1Mpa, air speed
CatH) and under the condition of 630 ℃ of reaction temperatures, reacting the conversion ratio that records iso-butane after 1 hour is 16%, and selective isobutene is 89.0% in the product.
Embodiment 3:
21.4 g copper nitrates and 38.6 g citric acids are dissolved in the 600 mL water, are made into the mixed solution of copper nitrate and citric acid, in above-mentioned solution, adding surface area is 1230 m
2g
-1, the most probable aperture is that unordered mesoporous carbon 158.8 g of 6.0 nm are (with reference to Journal of Materials Chemistry; 7764 pages of preparations of 2009 the 19th volume 7759 –); In 70 ℃ of waters bath with thermostatic control, stirred 10 minutes, through 120 ℃ of oven dry, roasting is 3 hours under 680 ℃ of blanket of nitrogen; Promptly get the CuO composite catalyst of mesoporous carbon load, measuring wherein, CuO quality percentage composition is 5.0%.The CuO composite catalyst of prepared mesoporous carbon load is packed in the fixed bed reactors, feed be preheated to 340 ℃ amount of substance than being the iso-butane of 1:6 and carbon dioxide gas mixture, be 5 L/ (g in 0.1Mpa, air speed
CatH) and under the condition of 630 ℃ of reaction temperatures, reacting the conversion ratio that records iso-butane after 1 hour is 48%, and selective isobutene is 90.4% in the product.
Embodiment 4:
74.4 g copper chlorides and 30.4 g citric acids are dissolved in the 600 mL water, are made into the mixed solution of copper chloride and citric acid, in above-mentioned solution, adding surface area is 1230 m
2g
-1, the most probable aperture is that unordered mesoporous carbon 176.8 g of 6.0 nm are (with reference to Journal of Materials Chemistry; 7764 pages of preparations of 2009 the 19th volume 7759 –); In 70 ℃ of waters bath with thermostatic control, stirred 10 minutes, through 120 ℃ of oven dry, roasting is 5 hours under 680 ℃ of blanket of nitrogen; Promptly get the CuO composite catalyst of mesoporous carbon load, measuring wherein, CuO quality percentage composition is 20.0%.The CuO composite catalyst of prepared mesoporous carbon load is packed in the fixed bed reactors, feed be preheated to 300 ℃ amount of substance than being the iso-butane of 1:4 and carbon dioxide gas mixture, be 4 L/ (g in 0.1Mpa, air speed
CatH) and under the condition of 630 ℃ of reaction temperatures, reacting the conversion ratio that records iso-butane after 1 hour is 42%, and selective isobutene is 86.0% in the product.
Embodiment 5:
30.3 g copper chlorides, 25.2 g lithium nitrates and 44.6 g citric acids are dissolved in the 600 mL water, are made into the mixed solution of copper chloride, lithium nitrate and citric acid, in above-mentioned solution, adding surface area is 1320 m
2g
-1, the most probable aperture is CMK-3 mesoporous carbon 158.8 g of 4.3 nm, in 70 ℃ of waters bath with thermostatic control, stirred 10 minutes, through 150 ℃ of oven dry; Roasting is 5 hours under 680 ℃ of blanket of nitrogen; Promptly get the CuO composite catalyst lithium modification, the mesoporous carbon load, measure wherein that CuO quality percentage composition is 9.7%, Li
2O quality percentage composition is 3.0%.The prepared composite catalyst is packed in the fixed bed reactors, feed be preheated to 340 ℃ amount of substance than being the iso-butane of 1:6 and carbon dioxide gas mixture, be 5 L/ (g in 0.1Mpa, air speed
CatH) and under the condition of 630 ℃ of reaction temperatures, reacting the conversion ratio that records iso-butane after 1 hour is 55%, and selective isobutene is 91.2%, reacts after 3 hours, and recording the iso-butane conversion ratio is 54%, and selective isobutene is 91.6%.
Embodiment 6:
42.4 g copper nitrates, 4.6g potassium nitrate and 44.6 g citric acids are dissolved in the 600 mL water, are made into the mixed solution of copper nitrate, potassium nitrate and citric acid, in above-mentioned solution, adding surface area is 1320 m
2g
-1, the most probable aperture is CMK-3 mesoporous carbon 158.8 g of 4.3 nm, in 70 ℃ of waters bath with thermostatic control, stirred 10 minutes, through 150 ℃ of oven dry; Roasting is 5 hours under 680 ℃ of blanket of nitrogen; Promptly get the CuO composite catalyst potassium modification, the mesoporous carbon load, measure wherein that CuO quality percentage composition is 9.9%, K
2O quality percentage composition is 1.2%.The CuO composite catalyst of prepared mesoporous carbon load is packed in the fixed bed reactors, feed be preheated to 340 ℃ amount of substance than being the iso-butane of 1:6 and carbon dioxide gas mixture, be 5 L/ (g in 0.1Mpa, air speed
CatH) and under the condition of 620 ℃ of reaction temperatures, reacting the conversion ratio that records iso-butane after 1 hour is 44%, and selective isobutene is 90.4%, reacts after 6 hours, and recording the iso-butane conversion ratio is 43%, and selective isobutene is 90.6%.
Claims (10)
1. the copper base metal oxide catalyst of a mesoporous carbon load, it is characterized in that: active component CuO counts 2 ~ 20% by the quality percentage composition, and auxiliary agent oxide mass percentage composition counts 0 ~ 3%, and all the other are mesoporous carbon.
2. catalyst according to claim 1 is characterized in that: said active component CuO is by quality percentage composition 5 ~ 20%, and said auxiliary agent oxide is selected from V
2O
5, Li
2O, MgO, K
2O, CaO, Ga
2O
3, ZnO, Al
2O
3, CeO
2Or La
2O
3In at least a.
3.. catalyst according to claim 2 is characterized in that: said auxiliary agent oxide is Li
2O or K
2O.
4. the preparation method of the described copper base metal oxide catalyst with the mesoporous carbon load of a claim 1 may further comprise the steps:
(1) takes by weighing the solvable inorganic salts of copper, the solvable inorganic salts and the citric acid of auxiliary agent; Be mixed with the aqueous solution of mantoquita; Be 3.0 ~ 24.0 g/L wherein in elemental copper atom concentration; The solvable inorganic salt concentration of auxiliary agent is counted 0 ~ 7.6 g/L by the metal atomic mass, and the solvable inorganic salts mass ratio of citric acid and copper is 0.4 ~ 2.0;
(2) in the above-mentioned aqueous solution, be that 0.016 ~ 0.255 ratio adds mesoporous carbon in copper and mesoporous carbon mass ratio, stirring, oven dry, roasting promptly get the copper base metal oxide catalyst of mesoporous carbon load.
5. preparation method according to claim 4 is characterized in that: said solvable inorganic salts are selected from acetate, sulfate, nitrate or halide salt.
6. according to the preparation method under the claim 5, it is characterized in that: said solvable inorganic salts are selected from acetate, nitrate or chlorate.
7. preparation method according to claim 4 is characterized in that: described mesoporous carbon, specific area are 1200 ~ 3100 m
2/ g, the most probable aperture is 2 ~ 8 nm, and pore volume is at 1.0 ~ 3.2 ml/g, and middle porosity is 75 ~ 100%.
8. preparation method according to claim 7 is characterized in that: described mesoporous carbon is selected from commodity CMK-1 with orderly pore structure, CMK-3, by unordered mesoporous carbon, CNT or the nanometer rods of organic carbon hydrate, metal halide carbonization preparation.
9. preparation method according to claim 4 is characterized in that: described roasting is through 500 ~ 750 ℃ of roastings 3 ~ 8 hours at inert atmosphere.
10. method according to claim 9 is characterized in that: described inert atmosphere is meant O
2Volumetric concentration is lower than 0.1% high-purity N
2, a kind of in high-purity Ar or the high-purity He gas.
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|---|---|---|---|---|
| CN102974379A (en) * | 2012-11-05 | 2013-03-20 | 南京大学 | Method for preparing nitrogen-doped photo-catalytic material containing gallium oxide at low temperature |
| CN103127935A (en) * | 2011-11-21 | 2013-06-05 | 中国石油化工股份有限公司 | Mesoporous carbon supported type copper-based catalyst, preparation method thereof and application thereof |
| CN103406123A (en) * | 2013-04-10 | 2013-11-27 | 长沙理工大学 | Preparation method and application of bamboo charcoal-loaded zinc oxide copper-doped composite catalyst material |
| CN104016342A (en) * | 2014-07-01 | 2014-09-03 | 青岛科技大学 | Method for preparing copper-based catalyst carrier |
| CN104437585A (en) * | 2013-09-22 | 2015-03-25 | 中国石油化工股份有限公司 | Copper oxide catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application of copper oxide catalyst |
| CN104437456A (en) * | 2013-09-22 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method and application of catalyst |
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| CN103406123A (en) * | 2013-04-10 | 2013-11-27 | 长沙理工大学 | Preparation method and application of bamboo charcoal-loaded zinc oxide copper-doped composite catalyst material |
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Inventor after: Liu Jingwei Inventor after: Han Lin Inventor after: Li Zezhuang Inventor after: Chen Shaohui Inventor after: Yang Aiwu Inventor after: Li Xiaoqiang Inventor after: Bai Jiye Inventor after: Liu Lijuan Inventor before: Liu Jingwei Inventor before: Han Lin Inventor before: Li Zezhuang Inventor before: Chen Shaohui Inventor before: Yang Aiwu Inventor before: Li Xiaoqiang Inventor before: Bai Jiye Inventor before: Liu Lijuan |
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Application publication date: 20121017 |