CN101966466A - Catalyst used in propane carbon for preparing propylene during dioxide dehydrogenation and preparation method thereof - Google Patents
Catalyst used in propane carbon for preparing propylene during dioxide dehydrogenation and preparation method thereof Download PDFInfo
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- CN101966466A CN101966466A CN2010102920664A CN201010292066A CN101966466A CN 101966466 A CN101966466 A CN 101966466A CN 2010102920664 A CN2010102920664 A CN 2010102920664A CN 201010292066 A CN201010292066 A CN 201010292066A CN 101966466 A CN101966466 A CN 101966466A
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- propane
- carbon dioxide
- chromium oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of heterogeneous catalysis, in particular to a preparation method of a catalyst used in a propane for preparing propylene in carbon dioxide dehydrogenation reaction and applications thereof. At present, the catalyst used in the dehydrogenation process generally has the defects of low activity, poor stability, low selectivity, high price, and the like. The invention obtains the catalyst by loading chromium oxide on NaZSM zeolite through an impregnation method, wherein the NaZSM zeolite has an atomic Si-Al ratio of 25-250 and the grain size of 0.1-5 mm. By using the catalyst in the ropane for preparing the propylene in the carbon dioxide dehydrogenation reaction, the invention has the advantages of simple operation, high activity, good selectivity and stability, low price, and the like.
Description
Technical field
The present invention the invention belongs to the chemical catalyst technical field, is specifically related to the Catalysts and its preparation method that a kind of propane and carbon dioxide dehydrogenation producing propylene is used.
Background technology
In recent years, because the fast development of propylene downstream product has greatly promoted the quick growth of China's propylene demand.According to estimates, China's propylene total productive capacity will reach 1,080 ten thousand tons/year in 2010, but China will reach 1,905 ten thousand tons to the demand of propylene, and insufficiency of supply-demand is 8,250,000 tons, and the propylene imbalance between supply and demand is very outstanding.Because the anxiety of petroleum resources relies on the steam cracking of oil and catalytic cracking technology can't satisfy the propylene demand that increases rapidly far away at present.There is abundant liquefied petroleum gas in China, and it is made up of 60% propane and 20% butane basically, if can effectively propane be changed into propylene by dehydrogenation, can alleviate the not enough problem in propylene source.So the propane catalytic dehydrogenation becomes current research focus, also be one of approach that solves propylene supply and demand problem.
The Oleflex technology of Uop Inc. and the Catofin technology of ABB Lummus company are mainly adopted in industrial propane catalytic dehydrogenation, and the former uses Pt-Sn/Al
2O
3Catalyst, the latter uses chromium oxide/aluminium oxide catalyst.But have still that catalysqt deactivation is very fast, regeneration is frequent, expend shortcoming such as a large amount of energy, be badly in need of new De-hydrogen Technology and improved.Carbon dioxide joins in the reaction gas, and compare advantage with pure dehydrogenation and dioxygen oxidation dehydrogenation producing propylene and be: (1) can improve equilibrium conversion; (2) reduce reaction temperature; (3) as the mild oxidation agent, prevent deep oxidation, guarantee the selectivity of product propylene; (4) remove carbon distribution, improve the stability of catalyst; (5) carbon dioxide is consumed as greenhouse gases, meets current environmental protection concept.
At present, shortcoming such as the catalyst ubiquity activity of propane and carbon dioxide dehydrogenation producing propylene is low, poor stability, selectivity are low, cost an arm and a leg has limited the industrialization of this technology.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method that activity is high, the propylene selectivity is high in the reaction of propane and carbon dioxide dehydrogenation producing propylene.
In addition, the present invention also provides the application of this catalyst in the reaction of propane and carbon dioxide dehydrogenation producing propylene.
Catalyst provided by the invention is a kind of support type chromium oxide catalyst, and the concrete steps of its preparation method are as follows:
(1) be that 25-250, crystallite dimension are that the NaZSM-5 zeolite of 0.1-5 mm joins Cr with the atom silica alumina ratio
3+Ion concentration is in the aqueous solution of chromium salt of 0.0005-0.007 g/mL, makes it form uniform suspension, and liquid-solid ratio is 5-50 mL/g;
(2) suspension is placed under the infrared lamp constantly and stir, until with solution evaporate to dryness, 80-110
oThe dry 10-40 h of C, 500-700 in the air atmosphere
oC roasting 3-20 h promptly obtains required support type chromium oxide catalyst.
Among the present invention, described chromic salts is preferably Cr (NO
3)
3Or CrCl
3Or Cr
2(SO
4)
3
Among the present invention, in the described support type chromium oxide catalyst, by weight percentage, preferable Cr content is 2%-7%.
Among the present invention, in the described support type chromium oxide catalyst, the preferable atom silica alumina ratio of NaZSM-5 Zeolite support is 60-130, and preferable crystallite dimension is 0.2-0.6 mm.
The invention allows for the application of described support type chromium oxide catalyst in the reaction of propane and carbon dioxide dehydrogenation producing propylene, its concrete reaction condition is as follows:
(1) described catalyst in nitrogen atmosphere in 500-700
oC activation 1-5 h;
(2) in reacting in flow reactor of fixed bed under the condition of normal pressure, total gas flow rate is 18--25 mL/min, and wherein the propane flow is 0.5-2 mL/min, and the flow of carbon dioxide is 0.5-5 mL/min, and all the other are nitrogen;
(3) described catalyst amount is 0.2-0.4 g, and the temperature of catalytic reaction is 500-650
oC, the reaction time is 1-8 h.
Catalyst provided by the invention and application advantage thereof are: method for preparing catalyst of the present invention is simple, cost is low; Catalyst activity height, reaction temperature are low; The propane dehydrogenation in carbonic anhydride condition reaction, propylene yield height.
The invention will be further elaborated below by embodiment.
The specific embodiment
Embodiment 1: add the TPAOH aqueous solution of 0.164 g sodium aluminate and 39 g 25% in 35 g water, after stirring 25 g TEOS are added drop-wise in the above-mentioned solution, stir 6 h under the room temperature, be warming up to 50
oC also keeps 0.5 h to drive ethanol away, replenishes 5 mL water, and moving into has in the stainless steel autoclave of Teflon liner, 170
oC crystallization 2 days.Put into 100 after the filtering and washing
oThe baking oven inner drying of C spends the night, in air 600
oC roasting 6 h remove the template agent.The gained zeolite is in 80
oC adds 1 M sodium nitrate solution (1 g zeolite add solution 10 mL) ion-exchange three times, each 4 h, the Na-ZSM-5 zeolite that obtain the atom silica alumina ratio behind the suction filtration after the oven dry and be 62, crystallite dimension is about 0.4 mm.With Cr (NO
3)
3Water-soluble obtain solution, Cr
3+Concentration is 0.003 g/mL, is that the NaZSM-5 Zeolite support of 200-500nm joins in the above-mentioned solution with size distribution, makes it form uniform suspension, and liquid-solid ratio is 10.46 mL/g, suspension is placed under the infrared lamp constantly stir, until with solution evaporate to dryness, 100
oDry 12 h of C are in the air atmosphere 600
oC roasting 4 h obtain the zeolite-loaded chromium oxide catalyst of Na-ZSM-5, and the content of Cr is 3% in the catalyst.
Embodiment 2-6: each step and condition by embodiment 1 prepare catalyst, and the preparation condition of change comprises the content of Cr in the kind, catalyst of the silica alumina ratio that feeds intake, the chromic salts of synthetic ZSM-5 zeolite and the sintering temperature of catalyst, sees Table 1.
The preparation of the zeolite-loaded chromium oxide catalyst of table 1 Na-ZSM-5
| ? | The zeolite silica alumina ratio | Chromic salts | Cr content (%) | Sintering temperature ( oC) |
| Embodiment 2 | 62 | Cr(NO 3) 3 | 1 | 600 |
| Embodiment 3 | 62 | CrCl 3 | 7 | 600 |
| Embodiment 4 | 29 | Cr 2(SO 4) 3 | 3 | 650 |
| Embodiment 5 | 127 | CrCl 3 | 3 | 550 |
| Embodiment 6 | 223 | Cr(NO 3) 3 | 3 | 600 |
Comparative Examples 1: step and condition by embodiment 1 prepare g-Al
2O
3Supported chromium, the content of Cr is 3% in the catalyst.
Embodiment 7: above-mentioned catalyst is used for the reaction of propane and carbon dioxide dehydrogenation producing propylene, concrete reaction condition is as follows: catalyst amount 0.2 g, reaction pressure is 1 atm, the reaction gas total flow is 20 mL/min, wherein nitrogen flow is 18.5 mL/min, carbon dioxide flow is 1 mL/min, and the propane flow is 0.5 mL/min, and the reaction procatalyst is 550
oC activates 1 h, is reflected at 550
oC carries out, and the conversion of propane and the propylene selectivity of reacting behind 1 h and 8 h see Table 2.
The reactivity of table 2 catalyst and propylene selectivity
| ? | React the conversion ratio (%) behind 1 h | React the selectivity (%) behind 1 h | React the conversion ratio (%) behind 8 h | React the selectivity (%) behind 8 h |
| Embodiment 1 | 40.3 | 88.7 | 30.1 | 91.8 |
| Embodiment 2 | 31.7 | 92.6 | 24.6 | 93.8 |
| Embodiment 3 | 39.1 | 89.3 | 29.5 | 91.9 |
| Embodiment 4 | 28.9 | 92.4 | 20.4 | 93.5 |
| Embodiment 5 | 38.0 | 89.6 | 31.1 | 91.8 |
| Embodiment 6 | 17.6 | 94.5 | 14.6 | 96.6 |
| Comparative Examples 1 | 24.2 | 92.5 | 16.4 | 94.6 |
Claims (5)
1. Preparation of catalysts method that the propane and carbon dioxide dehydrogenation producing propylene is used is characterized in that concrete steps are:
(1) be that 25-250, crystallite dimension are that the NaZSM-5 zeolite of 0.1-5 mm joins Cr with the atom silica alumina ratio
3+Ion concentration is in the aqueous solution of chromium salt of 0.0005-0.007 g/mL, makes it form uniform suspension, and liquid-solid ratio is 5-50 mL/g;
(2) suspension is placed under the infrared lamp constantly and stir, until with solution evaporate to dryness, 80-110
oThe dry 10-40 h of C, 500-700 in the air atmosphere
oC roasting 3-20 h promptly obtains required support type chromium oxide catalyst.
2. according to the described preparation method of claim 1, it is characterized in that described chromic salts is Cr (NO
3)
3Or CrCl
3Or Cr
2(SO
4)
3
3. according to the described preparation method of claim 1, it is characterized in that in the described support type chromium oxide catalyst that by weight percentage, Cr content is 0.5%-10%.
4. the support type chromium oxide catalyst for preparing as preparation method as described in one of claim 1-3.
5. the application of support type chromium oxide catalyst as claimed in claim 4 in the reaction of propane and carbon dioxide dehydrogenation producing propylene is characterized in that concrete reaction condition is as follows:
(1) with described catalyst in nitrogen atmosphere in 500-700
oC activation 1-5 h;
(2) in reacting in flow reactor of fixed bed under the condition of normal pressure, total gas flow rate is 18--25mL/min, and wherein the propane flow is 0.5-2 mL/min, and the flow of carbon dioxide is 0.5-5 mL/min, and all the other are nitrogen;
(3) described catalyst amount is 0.2-0.4 g, and the temperature of catalytic reaction is 500-650
oC, the reaction time is 1-8 h.
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|---|---|---|---|
| CN2010102920664A CN101966466A (en) | 2010-09-26 | 2010-09-26 | Catalyst used in propane carbon for preparing propylene during dioxide dehydrogenation and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607235A (en) * | 2015-01-13 | 2015-05-13 | 大连理工大学 | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation |
| CN104785286A (en) * | 2015-04-23 | 2015-07-22 | 中国科学院大连化学物理研究所 | Light hydrocarbon and carbon dioxide conversion catalyst, as well as preparation method and application thereof |
| CN105080596A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Isobutane oxidation dehydrogenation catalyst and preparation method and application method thereof |
| CN107537556A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Dehydrogenation of isobutane catalyst and its method in the presence of carbon dioxide mild oxidizing agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206033C (en) * | 2002-11-04 | 2005-06-15 | 大庆油田有限责任公司 | Catalyzer for preparing gasoline and liquefied gas from light hydrocarbon and preparation method |
| CN101342494A (en) * | 2008-08-28 | 2009-01-14 | 复旦大学 | Process for preparing catalyst for preparing propylene with propane dehydrogenation in carbonic anhydride condition and uses thereof |
-
2010
- 2010-09-26 CN CN2010102920664A patent/CN101966466A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206033C (en) * | 2002-11-04 | 2005-06-15 | 大庆油田有限责任公司 | Catalyzer for preparing gasoline and liquefied gas from light hydrocarbon and preparation method |
| CN101342494A (en) * | 2008-08-28 | 2009-01-14 | 复旦大学 | Process for preparing catalyst for preparing propylene with propane dehydrogenation in carbonic anhydride condition and uses thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080596A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Isobutane oxidation dehydrogenation catalyst and preparation method and application method thereof |
| CN104607235A (en) * | 2015-01-13 | 2015-05-13 | 大连理工大学 | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation |
| CN104607235B (en) * | 2015-01-13 | 2017-02-22 | 大连理工大学 | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation |
| CN104785286A (en) * | 2015-04-23 | 2015-07-22 | 中国科学院大连化学物理研究所 | Light hydrocarbon and carbon dioxide conversion catalyst, as well as preparation method and application thereof |
| CN107537556A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Dehydrogenation of isobutane catalyst and its method in the presence of carbon dioxide mild oxidizing agent |
| CN107537556B (en) * | 2016-06-29 | 2020-09-04 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst in presence of carbon dioxide mild oxidant and method thereof |
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Application publication date: 20110209 |