CN1696085A - Method for preparing propylene through oxydehydrogenation of propane and carbon dioxide - Google Patents
Method for preparing propylene through oxydehydrogenation of propane and carbon dioxide Download PDFInfo
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- CN1696085A CN1696085A CNA2005100255069A CN200510025506A CN1696085A CN 1696085 A CN1696085 A CN 1696085A CN A2005100255069 A CNA2005100255069 A CN A2005100255069A CN 200510025506 A CN200510025506 A CN 200510025506A CN 1696085 A CN1696085 A CN 1696085A
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- propane
- catalyzer
- carbon dioxide
- propylene
- reaction
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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
Abstract
A process for preparing propene from propane and CO2 by oxidizing and dehydrogenating features that its catalyst with high activity and stability is prepared from carrier (HZSM-5 zeolite with high Si/Al ratio) and active component (gallium oxide) through dipping.
Description
Technical field
The present invention relates to a kind of propane ZSM-5 zeolite with high silica alumina ratio under carbon dioxide atmosphere is carrier, and gallium oxide is the method for the Preparation of Catalyst propylene of active ingredient.
Background technology
Propylene is an intermediate important in the petrochemical complex, and it is the raw material of multiple products such as synthetic polypropylene, polyacrylonitrile, propenal, vinylformic acid.Therefore, the demand of propylene is very big for a long time, and the propylene that steam cracking and FCC produce far can not be met the need of market.Along with the exhaustion of global petroleum resources, utilize in the Sweet natural gas dehydrogenating propane synthesizing propylene to be paid close attention to by people gradually.
Though dehydrogenating propane process industrialization, but this process has certain limitation, owing to be subjected to thermodynamics equilibrium limit, reaction must be carried out under high temperature, low pressure, cause catalyst deactivation to be accelerated, energy consumption of reaction increases, and it is compared with pure dehydrogenation and dioxygen oxidation preparing propylene by dehydrogenating, and carbonic acid gas carries out oxidative dehydrogenation of propane as oxygenant and has following advantage: (1) provides the part energy as a kind of oxygenant of gentleness for the dehydrogenating propane thermo-negative reaction; (2) improve the equilibrium conversion of this reaction; (3) slow down catalyst deactivation.What is more important, CO
2Selective oxidation propane can be eliminated some greenhouse gases CO when effectively utilizing Sweet natural gas
2Thereby, solve the CO of enterprise such as long-standing chemical industry, petrochemical industry to a certain extent
2Emission problem, have very big social benefit.
Ga
2O
3And Ga
2O
3/ TiO
2The low-carbon alkanes carbonic acid gas oxydehydrogenation that is considered to be found at present prepares catalyzer preferably (K.Nakagawa et al, Chem.Commun.1998,1025 of low-carbon alkene reaction; K.Nakagawa et al, J.Catal., 2001,203,87; P.Michorezyk et al, Appl.Catal., 2003,251,425), they have high reaction activity and high.The non-constant of the stability of these catalyzer can't be promoted in industry.The catalyzer that lacks excellent property is a present preparing propylene through oxydehydrogenation of propane and carbon dioxide field existing questions.
Summary of the invention
The method that the purpose of this invention is to provide a kind of productive rate height, active high, preparing propylene through oxydehydrogenation of propane and carbon dioxide that stability is high.
The method of the propane and carbon dioxide preparing propylene by dehydrogenating that the present invention proposes, propane are being that carrier, gallium oxide are that reaction obtains under the catalyzer of active ingredient with high silica alumina ratio HZSM-5 zeolite under carbon dioxide atmosphere, and concrete steps and condition are:
(1) catalyzer was 550～750 ℃ of following oxygen activation 0.5～10 hour, and 350～650 ℃ of following hydrogen activate 0.5～10 hour then;
(2) propane, carbonic acid gas enter reactor reaction under nitrogen carrier gas, 500～700 ℃ of temperature of reaction, and the molar percentage of propane, feed carbon dioxide is respectively 2.5～10%, 5～20%, and all the other are carrier gas, and total flux is 20mL/min;
(3) consumption of above-mentioned reaction time catalizer is 0.1～0.5g.
Among the present invention, the carrier of catalyzer is a silica alumina ratio greater than 200 HZSM-5 zeolite.
Among the present invention, activity of such catalysts component Ga
2O
3Charge capacity be 0.5～20wt%.
Among the present invention, the Preparation of catalysts method is as follows:
(1) with Ga
2O
3Presoma is soluble in water, obtains solution a;
(2) the HZSM-5 zeolite is joined among the solution a, mix the formation slurries.The solid-to-liquid ratio of every gram is 5-100mL/g during interpolation;
(3) with above-mentioned slurries under air atmosphere in 60-110 ℃ of dry 5-40 hour, in the air atmosphere 350-750 ℃ roasting 3-30 hour.
Among the present invention, Ga
2O
3Presoma is Ga (NO
3)
3Or GaCl
3
The outstanding advantage of method provided by the invention is:
1, the present invention utilizes the Preparation of Catalyst propylene of prior art, reduces cost, and raises the efficiency.
2, propane and carbon dioxide oxidative dehydrogenation of the present invention, the productive rate height of propylene.
3, the good stability of catalyzer of the present invention in reaction is difficult for inactivation.
Embodiment
Example 1: the HZSM-5 with Si/Al=284 is a carrier, Ga (NO
3)
3Be presoma, with solid-to-liquid ratio 50mL/g dipping 5wt%Ga
2O
3, 110 ℃ of dryings 10 hours, 600 ℃ of roastings 6 hours obtain catalyzer-1, and are measuring its CO on the microreactor continuously
2Dehydrogenating propane activity under the atmosphere.Concrete reflection condition is as follows: catalyst levels 200mg, carrier gas high pure nitrogen flow are that the 20mL/min. catalyzer activates 0.5h with oxygen earlier down at 550 ℃, activate 0.5h with hydrogen then under 350 ℃, are reflected under 600 ℃ and carry out.The propane molar content is 2.5% in the reaction gas, and the carbonic acid gas molar content is 5% (mol ratio C
3H
8: CO
2=1: 2), residual gas is a high pure nitrogen.The yield of propylene is 25.7% on catalyzer during stable state-1, and the propylene selectivity is 57.3%.
Example 2: the HZSM-5 with Si/Al=500 is a carrier, Ga (NO
3)
3Be presoma, solid-to-liquid ratio is flooded 5wt%Ga with 10mL/g
2O
3, 60 ℃ of dryings 30 hours, 450 ℃ of roastings 20 hours obtain catalyzer-2, utilize the method for example 1 to measure its CO
2Dehydrogenating propane activity under the atmosphere.The yield of propylene is 24.7% on catalyzer during stable state-2, and the propylene selectivity is 64.8%.
Example 3: utilize the method for example 1 to measure catalyzer-1 at CO
2The stability of the propylene dehydrogenation reaction under the atmosphere reacts that the yield of propylene is 24.1% after 100 hours, and the propane selectivity is 62.7%.
Example 4: utilize the method for example 1 to measure catalyzer-2 at CO
2The stability of dehydrogenating propane under atmosphere reaction reacts that the yield of propylene is 21.9% after 100 hours, and the propylene selectivity is 72.3%.
Example 5: the HZSM-5 with Si/Al=284 is a carrier, Ga (NO
3)
3Be presoma, solid-to-liquid ratio is flooded 1wt%Ga with 10mL/g
2O
3, 60 ℃ of dryings 30 hours, 450 ℃ of roastings 20 hours obtain catalyzer-3, utilize the method for example 1 to measure its CO
2Dehydrogenating propane activity under the atmosphere.The yield of propylene is 21.6% on catalyzer during stable state-3, and the propylene selectivity is 62.5%.
Example 6: utilize the method for example 5 to measure catalyzer-3 at CO
2The stability of dehydrogenating propane under atmosphere reaction reacts that the yield of propylene is 17.9% after 100 hours, and the propylene selectivity is 70.7%.
Example 7: the HZSM-5 with Si/Al=284 is a carrier, Ga (NO
3)
3Be presoma, solid-to-liquid ratio is flooded 10wt%Ga with 50mL/g
2O
3, 110 ℃ of dryings 10 hours, 650 ℃ of roastings 6 hours obtain catalyzer-4, utilize the method for example 1 to measure its CO
2Dehydrogenating propane activity under the atmosphere.The yield of propylene is 28.2% on catalyzer during stable state-4, and the propylene selectivity is 62.1%.
Example 8: utilize the method for example 1 to measure catalyzer-1, and measuring its CO on the microreactor continuously
2Dehydrogenating propane activity under the atmosphere.Concrete reflection condition is as follows: catalyst levels 500mg, carrier gas high pure nitrogen flow are that the 20mL/min. catalyzer activates 10 hours with oxygen earlier down at 750 ℃, activate 10 hours with hydrogen then under 550 ℃, are reflected under 600 ℃ and carry out.The propane molar content is 10% in the reaction gas, and the carbonic acid gas molar content is 20% (mol ratio C
3H
8: CO
2=1: 2), residual gas is a high pure nitrogen.The yield of propylene is 18.7% on catalyzer during stable state-1, and the propylene selectivity is 67.4%.
Comparative Examples 1: the HZSM-5 with Si/Al=120 is a carrier, Ga (NO
3)
3Be presoma, dipping 5wt%Ga
2O
3, 100 ℃ of dryings 20 hours, 600 ℃ of roastings 3 hours obtain comparative catalyst-1, utilize the method for example 1 to measure its CO
2Dehydrogenating propane activity under the atmosphere.The yield of propylene is 20.0% on comparative catalyst during stable state-1, and the propylene selectivity is 35.0%.React after 20 hours, the yield of propylene is 9.2% on the catalyzer, and the propylene selectivity is 69.8%.
Comparative Examples 2: with Ga (NO
3)
3Be presoma, 600 ℃ of direct roasting 6 hours obtain Ga
2O
3Catalyzer utilizes the method for example 1 to measure its CO
2Dehydrogenating propane activity under the atmosphere.The yield of reacting propylene on 6 hours rear catalysts is 30.0%, but the propylene selectivity is 31.2%.
Comparative Examples 3: with TiO
2(Degussa P25) is carrier, Ga (NO
3)
3Be presoma, dipping 5wt%Ga
2O
3, 100 ℃ of dryings 20 hours, 600 ℃ of roastings 6 hours obtain Ga
2O
3/ TiO
2Catalyzer utilizes the method for example 1 to measure its CO
2Dehydrogenating propane activity under the atmosphere.React that the yield of propylene is 1.0% after 3 hours, the propylene selectivity is 89%.
Claims (5)
1, a kind of method of preparing propylene through oxydehydrogenation of propane and carbon dioxide is characterized in that propane is being that carrier, gallium oxide are that reaction obtains under the catalyzer of active ingredient with high silica alumina ratio HZSM-5 zeolite under carbon dioxide atmosphere, concrete steps and condition are:
(1) catalyzer was 550～750 ℃ of following oxygen activation 0.5～10 hour, and 350～650 ℃ of following hydrogen activate 0.5～10 hour then;
(2) propane, carbonic acid gas enter reactor reaction under nitrogen carrier gas, 500～700 ℃ of temperature of reaction, and the molar percentage of propane, feed carbon dioxide is respectively 2.5～10%, 5～20%, and all the other are carrier gas, and total flux is 20mL/min;
(3) consumption of above-mentioned reaction time catalizer is 0.1～0.5g.
2, method according to claim 1, the carrier that it is characterized by catalyzer are silica alumina ratio greater than 200 HZSM-5 zeolite.
3, method according to claim 1 is characterized by activity of such catalysts component Ga
2O
3Charge capacity be 0.5～20wt%.
4, Preparation of catalysts method according to claim 1 is characterized in that:
(1) with Ga
2O
3Presoma is soluble in water, obtains solution a;
(2) the HZSM-5 zeolite is joined among the solution a, mix the formation slurries, the solid-to-liquid ratio of every gram is 5-100mL/g during interpolation;
(3) with above-mentioned slurries under air atmosphere in 60-110 ℃ of dry 5-40 hour, in the air atmosphere 350-750 ℃ roasting 3-30 hour.
5, Preparation of catalysts method according to claim 4 is characterized in that Ga
2O
3Presoma is Ga (NO
3)
3Or GaCl
3
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100255069A CN1321098C (en) | 2005-04-28 | 2005-04-28 | Method for preparing propylene through oxydehydrogenation of propane and carbon dioxide |
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|---|---|---|---|
| CNB2005100255069A CN1321098C (en) | 2005-04-28 | 2005-04-28 | Method for preparing propylene through oxydehydrogenation of propane and carbon dioxide |
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|---|---|
| CN1696085A true CN1696085A (en) | 2005-11-16 |
| CN1321098C CN1321098C (en) | 2007-06-13 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101342494B (en) * | 2008-08-28 | 2011-08-03 | 复旦大学 | Process for preparing catalyst for preparing propylene with propane dehydrogenation in carbonic anhydride condition and uses thereof |
| CN101785993B (en) * | 2009-01-22 | 2012-09-05 | 复旦大学 | Preparation method of catalyst for producing propylene by propane dehydrogenation under carbon dioxide atmosphere |
| CN105396571A (en) * | 2014-09-16 | 2016-03-16 | 中国石油化工股份有限公司 | Mesoporous Ga/Al composite oxide catalyst, preparation method and applications thereof |
| CN108409524A (en) * | 2018-03-14 | 2018-08-17 | 福州大学 | A method of promote oxidative dehydrogenation of propane to prepare propylene using coal |
| CN109126855A (en) * | 2018-09-25 | 2019-01-04 | 陕西师范大学 | A kind of support type GaN catalyst and its in catalysis CO2Application in propane oxide dehydrogenation reaction |
| CN109603898A (en) * | 2017-10-17 | 2019-04-12 | 苏州大学 | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for preparing low-carbon alkene |
| CN114797951A (en) * | 2021-01-27 | 2022-07-29 | 中国科学院大连化学物理研究所 | Catalyst for weakening excessive oxidation and enhancing C-H bond activation, preparation and application |
| CN115957738A (en) * | 2023-01-03 | 2023-04-14 | 大连理工大学 | Preparation method and application of catalyst for preparing propylene by propane dehydrogenation |
| CN115957738B (en) * | 2023-01-03 | 2024-05-10 | 大连理工大学 | Preparation method and application of catalyst for preparing propylene by propane dehydrogenation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5229967B2 (en) * | 1973-05-23 | 1977-08-05 | ||
| JPH0427014A (en) * | 1990-05-23 | 1992-01-30 | Taisei Corp | Construction of underground structure |
| WO2000048971A1 (en) * | 1999-02-22 | 2000-08-24 | Symyx Technologies, Inc. | Compositions comprising nickel and their use as catalyst in oxidative dehydrogenation of alkanes |
| CN1201861C (en) * | 2003-07-15 | 2005-05-18 | 南京大学 | Catalyst for producing propene from propane by selective carbon dioxide oxidation |
-
2005
- 2005-04-28 CN CNB2005100255069A patent/CN1321098C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101342494B (en) * | 2008-08-28 | 2011-08-03 | 复旦大学 | Process for preparing catalyst for preparing propylene with propane dehydrogenation in carbonic anhydride condition and uses thereof |
| CN101785993B (en) * | 2009-01-22 | 2012-09-05 | 复旦大学 | Preparation method of catalyst for producing propylene by propane dehydrogenation under carbon dioxide atmosphere |
| CN105396571A (en) * | 2014-09-16 | 2016-03-16 | 中国石油化工股份有限公司 | Mesoporous Ga/Al composite oxide catalyst, preparation method and applications thereof |
| CN109603898A (en) * | 2017-10-17 | 2019-04-12 | 苏州大学 | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for preparing low-carbon alkene |
| CN109603898B (en) * | 2017-10-17 | 2021-12-21 | 苏州大学 | Low-carbon alkane dehydrogenation catalyst and method for preparing low-carbon olefin |
| CN108409524A (en) * | 2018-03-14 | 2018-08-17 | 福州大学 | A method of promote oxidative dehydrogenation of propane to prepare propylene using coal |
| CN108409524B (en) * | 2018-03-14 | 2020-12-25 | 福州大学 | Method for preparing propylene by using coal to promote oxidative dehydrogenation of propane |
| CN109126855A (en) * | 2018-09-25 | 2019-01-04 | 陕西师范大学 | A kind of support type GaN catalyst and its in catalysis CO2Application in propane oxide dehydrogenation reaction |
| CN109126855B (en) * | 2018-09-25 | 2020-12-18 | 陕西师范大学 | Supported GaN catalyst and application thereof in catalyzing CO2Application of oxidative propane dehydrogenation reaction |
| CN114797951A (en) * | 2021-01-27 | 2022-07-29 | 中国科学院大连化学物理研究所 | Catalyst for weakening excessive oxidation and enhancing C-H bond activation, preparation and application |
| CN115957738A (en) * | 2023-01-03 | 2023-04-14 | 大连理工大学 | Preparation method and application of catalyst for preparing propylene by propane dehydrogenation |
| CN115957738B (en) * | 2023-01-03 | 2024-05-10 | 大连理工大学 | Preparation method and application of catalyst for preparing propylene by propane dehydrogenation |
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| Publication number | Publication date |
|---|---|
| CN1321098C (en) | 2007-06-13 |
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Granted publication date: 20070613 Termination date: 20100428 |