CN102826949A - Novel method for preparing isobutene by iso-butane dehydrogenation - Google Patents
Novel method for preparing isobutene by iso-butane dehydrogenation Download PDFInfo
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- CN102826949A CN102826949A CN2012103334645A CN201210333464A CN102826949A CN 102826949 A CN102826949 A CN 102826949A CN 2012103334645 A CN2012103334645 A CN 2012103334645A CN 201210333464 A CN201210333464 A CN 201210333464A CN 102826949 A CN102826949 A CN 102826949A
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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
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- 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
The invention relates to the technical field of chemistry and chemical engineering, which specifically relates to a novel method for preparing isobutene by iso-butane dehydrogenation; the novel method concretely comprises the following steps: making inert gas as emptying gas; making iso-butane as raw material; using V/CNTs as catalyst; processing catalytic dehydrogenation reaction at 480-620 degrees centigrade under 0.05-1.0MPa, wherein vanadium (atoms) loading mass of the V/CNTs catalyst is equal to 3-11wt%; and the gas hourly space velocity of the iso-butane is 10-1000h<-1>. According to the invention, catalyst used in a preparation method is characterized by friendly environment and relatively coat; in addition, the result of iso-butane conversion ratio and isobutene selectivity is close to a result when industrial chrome-aluminum catalyst is used.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, being specifically related to a kind of is the novel method of feedstock production iso-butylene with the Trimethylmethane.
Background technology
Iso-butylene is a kind of important chemical material, and molecular formula is C
4H
8Global range is interior very big to the demand of iso-butylene, and is the trend of cumulative year after year.Traditional iso-butylene production is mainly extracted from oil catalytic cracking unit and petroleum naphtha CCU by product, but iso-butylene all is as co-production in these methods, and output is limited by the scale and the C4 olefins yield of main reaction.China's liquefied gas aboundresources, wherein Trimethylmethane is as a kind of staple, and its major part does not obtain reasonable use along with liquefied gas is consumed as domestic fuel.Therefore adopt Trimethylmethane as raw material, prepare iso-butylene through dehydrogenation reaction and have inborn advantage and social effect.
Since nineteen sixties; Offshore company begins to develop the catalyzer and the catalytic dehydrogenation process of preparing isobutene through dehydrogenation of iso-butane in succession, and is representative and realized the FBD-4 technology of the industrialized Snamprogetti of comprising company, Catofin technology, the Oleflex technology of UOP, the STAR technology of Phillips and the Linde technology of Linde AG etc. of Lummus/UCI exploitation.Their employed catalyzer mainly is divided into two types: a kind of is that chromic oxide is loaded on the alumina supporter, and also having a kind of is that precious metals pt is loaded on aluminum oxide or other carriers.When it was applied to catalytic dehydrogenation, temperature of reaction was between 500-650 ℃, and reaction pressure is between 0.1-6.0MPa, and the Trimethylmethane transformation efficiency is between 40-60%, and the selectivity of iso-butylene is between 91-95%.Though these technologies have realized industriallization at present, but high toxicity and two types of common characteristics that are prone to inactivation of catalyzer expensive, chromium metal of precious metal are still impelling people to seek more suitably catalyzer.
Vanadium metal and chromium metal are adjacent in the periodic table of elements, on multivalence attitude and oxidisability, have similarity, but its toxicity is lower, and environmental pollution property is littler, and therefore industry is gone up vanadium catalyst and has been used to reactions such as preparing sulfuric acid by oxidizing sulfur dioxide, pure oxidation system aldehyde; Simultaneously also having a lot of scholars and mechanism to study is used for dehydrogenating low-carbon alkane with vanadium, attempts with its alternative platinum catalyst and chrome catalysts.
Carbon nanotube (CNTs) is one type and incites somebody to action
Sp 2 The novel carbon element nano material that the class graphite plane that one C constitutes combines by certain way.In recent years, grow with each passing day with the research of carbon nanotube as support of the catalyst or promotor, the Application Areas that preferentially relates to comprises processes such as selecting hydrogenation, dehydrogenation, hydrogenolysis.Consider from the chemical catalysis angle, carbon nanotube except that the tube wall with high mechanical strength, graphite-like structure, nano level tube chamber and big and modifiable surface, its good electron transport performance, to H
2Strong adsorption activation ability and to absorption hydrogen characteristic such as issuable promoter action of overflow on catalyzer; Make its some support of the catalyst than routine (gac, aluminum oxide, silicon oxide etc.) have more characteristics, this increases its application chance at catalytic field greatly.
Existing bibliographical information uses carbon nanotube loaded barium oxide as catalyst for reduction of oxides of nitrogen, but it is then rarely found that this catalyzer is used for the dehydrating alkanes reaction.
Summary of the invention
What the object of the present invention is to provide that a kind of dehydrogenation of isobutane transformation efficiency is high, selective isobutene is high prepares the method for iso-butylene by dehydrogenation of isobutane.
Preparing method proposed by the invention is a raw material with the Trimethylmethane, adopts carbon nanotube loaded vanadium oxide as catalyzer, in fixed bed or fluidized-bed, and catalyzing iso-butane alkane dehydrogenation preparing isobutene.
The novel method of a kind of preparing isobutene through dehydrogenation of iso-butane provided by the invention, concrete steps are following:
With the rare gas element is vent gas, is raw material with the Trimethylmethane, and employing V/CNTs is a catalyzer, catalytic dehydrogenating reaction under 0.05 – 1.0MPa pressure, 480-620 ℃ temperature; The vanadium atom load quality accounts for 3wt%-11wt% in the wherein said V/CNTs catalyzer, and the gas hourly space velocity of Trimethylmethane is 10-1000h
-1
Among the present invention, said rare gas element is N
2Or Ar.
Among the present invention, vanadium atom mass loading amount is 3wt%-11wt% in the said V/CNTs catalyzer.
Among the present invention, said V/CNTs catalyzer is the 20-30 order.
Among the present invention; Said V/CNTs Preparation of catalysts method is following: carbon nanotube (CNTs) is immersed in ammonium meta-vanadate and the oxalic acid solution; After 60-120 ℃ of drying under vacuum or the normal pressure; After under the 500-620 ℃ of nitrogen atmosphere roasting 2-8 hour, obtain after roasting 3-6 hour in 200-300 under the air atmosphere ℃ again, wherein; The mass ratio of said carbon nanotube and ammonium meta-vanadate calculates according to the catalyzer vanadium atom mass content of required preparation, and the mol ratio of ammonium meta-vanadate and oxalic acid is 1:1.5-1:2.0.
The invention has the advantages that employed catalyzer environment is friendly among the preparation method, cost is lower, and is close when and the result of Trimethylmethane transformation efficiency and selective isobutene and the industrial chromium of use-Al catalysts.
Embodiment
Below in conjunction with embodiment the present invention is done further explain.
Among the embodiment, carbon nanotube is bought from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.Carbon nanotube external diameter 20-30 nanometer, pipe range 10-30 micron.
Embodiment 1
Adopt the 5%V/CNTs catalyzer of immersion process for preparing to place the stainless steel tube fixed-bed reactor of a diameter 10mm 2.0 grams, vanadium atom mass loading amount is 5.0% in the catalyzer.Catalyst preparation step is following:
Dissolving 0.757 gram ammonium meta-vanadate and 2.0 gram oxalic acid in 4.5 ml waters; The dissolving back adds 6.0 gram carbon nanotubes fully; At room temperature left standstill after stirring 12 hours, and placed 90 ℃ of baking ovens to dry afterwards, place the following 620 ℃ of roastings of tube furnace nitrogen atmosphere after 5 hours in sample then; 200 ℃ of roastings obtain catalyzer 1 in the air after 5 hours, get 20 –, 30 order particles after the granulation.
As vent gas, as raw material, gas hourly space velocity is 530h with pure Trimethylmethane with nitrogen
-1, being reflected under the normal pressure and carrying out, temperature is 480 ℃.The Trimethylmethane transformation efficiency is 25.5%, is 95.0% to selective isobutene, and the iso-butylene yield is 24.2%.
Embodiment 2
Adopt the 7%V/CNTs catalyzer of immersion process for preparing to place the stainless steel tube fixed-bed reactor of a diameter 10mm 2.0 grams, vanadium atom mass loading amount is 7.0% in the catalyzer.Catalyst preparation step is following:
Dissolving 1.103 gram ammonium meta-vanadates and 2.5 gram oxalic acid in 4.5 ml waters; The dissolving back adds 6.0 gram carbon nanotubes fully; At room temperature left standstill after stirring 12 hours, and placed 90 ℃ of baking ovens to dry afterwards, place the following 620 ℃ of roastings of tube furnace nitrogen atmosphere after 5 hours in sample then; 250 ℃ of roastings obtain catalyzer 2 in the air after 5 hours, get 20 –, 30 order particles after the granulation.
As vent gas, as raw material, gas hourly space velocity is 530h with pure Trimethylmethane with nitrogen
-1, being reflected under the normal pressure and carrying out, temperature is 550 ℃.The Trimethylmethane transformation efficiency is 54.0%, and selective isobutene is 92.0%, iso-butylene yield 49.7%.
The experiment proof is an optimum reaction condition at this moment.
Embodiment 3
Adopt the 3%V/CNTs catalyzer of immersion process for preparing to place the stainless steel tube reactor drum of a diameter 10mm 2.0 grams, vanadium atom mass loading amount is 3.0% in the catalyzer.Catalyst preparation step is following:
Dissolving 0.437 gram ammonium meta-vanadate and 2.0 gram oxalic acid in 4.5 ml waters; The dissolving back adds 6.0 gram carbon nanotubes fully; At room temperature left standstill after stirring 12 hours, and placed 90 ℃ of baking ovens to dry afterwards, place the following 620 ℃ of roastings of tube furnace nitrogen atmosphere after 2.5 hours in sample then; 300 ℃ of roastings obtain catalyzer 3 in the air after 6 hours, get 20 –, 30 order particles after the granulation.
As vent gas, as raw material, gas hourly space velocity is 10h with pure Trimethylmethane with nitrogen
-1, reaction pressure is 1.0MPa, temperature is 620 ℃.The Trimethylmethane transformation efficiency is 49.2%, is 86.5% to selective isobutene, and the iso-butylene yield is 42.6%.
Embodiment 4
Adopt the 11%V/CNTs catalyzer of immersion process for preparing to place the stainless steel tube reactor drum of a diameter 10mm 2.0 grams, vanadium atom mass loading amount is 5.0% in the catalyzer.Catalyst preparation step is following:
Dissolving 1.888 gram ammonium meta-vanadates and 3.7 gram oxalic acid in 4.5 ml waters; The dissolving back adds 6.0 gram carbon nanotubes fully; At room temperature left standstill after stirring 12 hours, and placed 90 ℃ of baking ovens to dry afterwards, place the following 620 ℃ of roastings of tube furnace nitrogen atmosphere after 8 hours in sample then; 250 ℃ of roastings obtain catalyzer 4 in the air after 3 hours, get 20 –, 30 order particles after the granulation.
As vent gas, as raw material, gas hourly space velocity is 900h with pure Trimethylmethane with nitrogen
-1, reaction pressure is 0.5MPa, temperature is 550 ℃.The Trimethylmethane transformation efficiency is 39.4%, is 92.5% to selective isobutene, and the iso-butylene yield is 36.4%.
Claims (6)
1. the novel method of a preparing isobutene through dehydrogenation of iso-butane is characterized in that concrete steps are following:
With the rare gas element is vent gas, is raw material with the Trimethylmethane, and employing V/CNTs is a catalyzer, catalytic dehydrogenating reaction under 0.05-1.0MPa pressure, 480-620 ℃ temperature; The vanadium atom load quality accounts for 3wt%-11wt% in the wherein said V/CNTs catalyzer, and the gas hourly space velocity of Trimethylmethane is 10-1000h
-1
2. the novel method of preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterized in that: said rare gas element is N
2Or Ar.
3. the novel method of preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterized in that: the vanadium atom load quality accounts for 3-11% in the said V/CNTs catalyzer.
4. the novel method of preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterized in that: said V/CNTs catalyzer is the 20-30 order.
5. the novel method of preparing isobutene through dehydrogenation of iso-butane according to claim 1; It is characterized in that; Said V/CNTs Preparation of catalysts method is following: carbon nanotube is immersed in ammonium meta-vanadate and the oxalic acid solution; After 60-120 ℃ of drying under vacuum or the normal pressure, after under the 500-620 ℃ of nitrogen atmosphere roasting 2-8 hour, obtain after roasting 3-6 hour in 200-300 under the air atmosphere ℃ again.
6. the novel method of preparing isobutene through dehydrogenation of iso-butane according to claim 4; The mass ratio that it is characterized in that said carbon nanotube and ammonium meta-vanadate calculates according to the catalyzer vanadium atom mass content of required preparation, and the mol ratio of ammonium meta-vanadate and oxalic acid is 1:1.5-1:2.0.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105130740A (en) * | 2015-08-05 | 2015-12-09 | 山东成泰化工有限公司 | Method for preparing isobutene from isobutane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211972A (en) * | 2010-04-06 | 2011-10-12 | 中国石油化工股份有限公司 | Application of hydrotalcite-based supported catalyst to preparation of isobutene from isobutane by dehydrogenating |
| CN102631914A (en) * | 2011-02-15 | 2012-08-15 | 中国石油化工股份有限公司 | Vanadium pentoxide catalyst taking mesoporous carbon as carrier, and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211972A (en) * | 2010-04-06 | 2011-10-12 | 中国石油化工股份有限公司 | Application of hydrotalcite-based supported catalyst to preparation of isobutene from isobutane by dehydrogenating |
| CN102631914A (en) * | 2011-02-15 | 2012-08-15 | 中国石油化工股份有限公司 | Vanadium pentoxide catalyst taking mesoporous carbon as carrier, and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130740A (en) * | 2015-08-05 | 2015-12-09 | 山东成泰化工有限公司 | Method for preparing isobutene from isobutane |
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