CN106365939A - Method for preparing isobutene - Google Patents
Method for preparing isobutene Download PDFInfo
- Publication number
- CN106365939A CN106365939A CN201610735050.3A CN201610735050A CN106365939A CN 106365939 A CN106365939 A CN 106365939A CN 201610735050 A CN201610735050 A CN 201610735050A CN 106365939 A CN106365939 A CN 106365939A
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- CN
- China
- Prior art keywords
- isobutene
- oxide
- preparation
- molecular sieve
- catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention discloses a method for preparing isobutene. The method comprises the steps that iso-butane, hydrogen and water vapor are mixed to obtain a gas mixture, wherein the molar ratio of iso-butane, hydrogen and water vapor is 1:0.2-0.3:4-6; the gas mixture enters a fixed bed reactor, and is in contact with dehydrogenation catalyst in the fixed bed reactor, wherein the reacting temperature is 800-1000 DEG C, the pressure is 2-5 Mpa, the hourly space velocity of the gas mixture is 100-1000, and then isobutene is obtained. According to the technical scheme, the method for preparing isobutene has the advantages that the percent conversion of iso-butane can reach 99.9%, the selectivity of isobutene is increased by 50%, the method is free of pollution; compared with the traditional production method, the energy consumption is reduced by 10%-20%, and the equipment investment is reduced by 10-40%.
Description
Technical field
The present invention relates to chemical industry synthesis field, more particularly, to a kind of preparation side preparing isobutene. using dehydrogenation of isobutane
Method.
Background technology
Isobutene. is the important source material of fine chemistry industry, and high-purity isobutylene is widely used as producing butyl rubber and poly- isobutyl
The monomer of alkene or intermediate are it is also possible to be used for producing the elastomers such as butyl rubber, isoprene rubber, polyisoamylene rubber, acceptable
For producing various fine chemicals.
A large amount of productions of the exploitation of isobutene. downstream product, especially mtbe, lead to the demand of isobutene. acute
Increase, the contradiction of the global inadequate resource of isobutene., expand isobutene. source, increase isobutene. yield, become the whole world
One important topic of petrochemical industry development.
Traditional isobutene. produces and mainly carries from oil catalytic cracking unit and Petroleum catalytic cracking unit by-product
Take, but in these methods, isobutene. is all as byproduct production, and yield is limited by the scale of primary response and c4 alkene produces
Rate., as a kind of main component, its major part is with liquefied gas as civilian combustion for China's liquefied gas aboundresources, wherein iso-butane
Material is consumed, and is not reasonably utilized.Therefore adopt iso-butane as raw material, isobutene. tool is prepared by dehydrogenation reaction
There are inborn advantage and social meaning.
The preparation method of existing isobutene. has that iso-butane conversion ratio is low, selective isobutene is poor, high energy consumption, equipment are thrown
The shortcomings of provide big.
Content of the invention
The technical problem to be solved in the present invention is for drawbacks described above, provides a kind of iso-butane to turn
Rate is high, and selective isobutene is high, and energy consumption is low, and equipment investment is little, the preparation method of the isobutene. of environmentally safe.
The present invention employs the following technical solutions: a kind of preparation method of isobutene., comprises the steps: raw material iso-butane
Form gaseous mixture with hydrogen, vapor, wherein iso-butane: hydrogen: the mol ratio of vapor is 1: 0.2-0.3:4- after mixing
6；
Reaction temperature 800-1000 DEG C, pressure 2-5mpa, gaseous mixture volume space velocity is 100-1000 hour-1, gaseous mixture enters solid
Fixed bed reactor, contacts with adding dehydrogenation in fixed bed reactors, obtains isobutene.；
Above-mentioned catalyst is by the material composition of following weight portion, stannum oxide 7-10 part, Zinc oxide particles 5-10 part, basic aluminum sulfate
4-6 part, manganese oxide particle 4-10 part, 3 parts of tungsten oxide, cocoanut active charcoal 5-8 part, attapulgite modified 4-8 part, five oxidations two
Vanadium 4-8 part, Tungstic anhydride. 4-6 part, aluminium oxide 5-8 part, amorphous silica-alumina 4-8 part, molecular sieve 6-7 part.
The following is further improvement of the present invention:
Described Zinc oxide particles mean particle diameter is 23nm；
The mean particle diameter of manganese oxide particle is 40nm.
Improve further:
Aluminium oxide be selected from boehmite, gibbsite, boehmite, γ-aluminium oxide, α-aluminium oxide, δ-aluminium oxide, θ-
Aluminium oxide or their mixture.
Improve further:
Described molecular sieve is the mixture of zsm-5, beta-zeolite molecular sieve and mfi molecular sieve, and mass ratio is 1-2:3-6:2-5.
Improve further:
The preparation method of above-mentioned catalyst is as follows:
1), by above-mentioned stannum oxide 7-10 part, Zinc oxide particles 5-10 part, basic aluminum sulfate 4-6 part, manganese oxide particle 4-10 part,
3 parts of tungsten oxide, cocoanut active charcoal 5-8 part, attapulgite modified 4-8 part, vanadic anhydride 4-8 part, Tungstic anhydride. 4-6 part, oxygen
Change aluminum 5-8 part, amorphous silica-alumina 4-8 part, molecular sieve 6-7 part mix homogeneously, compressing, obtain catalyst carrier；
2), adopt dipping solution impregnated catalyst support, through in hermetic container situ crystallization, before being dried to obtain catalyst
Drive body；
The reaction temperature of in-situ crystallization reaction is 35-80 DEG C, and the response time is 2-8 hour；
Baking temperature is 230-250 degree Celsius, vacuum drying, and vacuum is 0.8mpa.
3), by step 2) in catalyst precursor add plasma generator in, adjustment plasma generator work(
Rate is plasma-activated for carrying out during 800-1000w, and plasma activation time is 30-40min, prepared catalyst.
Improve further:
The preparation process of dipping solution is as follows, weighs molybdenum oxide and basic nickel carbonate, plus deionized water mix homogeneously, adds concentration
Phosphoric acid for 85%, is heated to 75 DEG C, and constant temperature one hour obtains bottle green clear transparent solutions, adds ammonium metatungstate and stir
Mix, after dissolving, obtain final product impregnation liquid.
The present invention has following technique effect using technique scheme, and up to 99.9%, isobutene. selects iso-butane conversion ratio
Selecting property improves 50%, and pollution-free, the more traditional production method of energy consumption reduces 10-20%, and equipment investment reduces 10-40%.
Specific embodiment
Embodiment, a kind of preparation method of isobutene., comprise the steps: to mix raw material iso-butane with hydrogen, vapor
Form gaseous mixture, wherein iso-butane: hydrogen: the mol ratio of vapor is 1: 0.2-0.3:4-6 after conjunction；Reaction temperature 800-
1000 DEG C, pressure 2-5mpa, gaseous mixture volume space velocity is 100-1000 hour-1, gaseous mixture enters fixed bed reactors, with fixation
Add dehydrogenation contact in bed reactor, obtain isobutene..
Above-mentioned catalyst is by the material composition of following weight portion, stannum oxide 7-10 part, Zinc oxide particles 5-10 part, alkaline sulfur
Sour aluminum 4-6 part, manganese oxide particle 4-10 part, 3 parts of tungsten oxide, cocoanut active charcoal 5-8 part, attapulgite modified 4-8 part, five oxygen
Change two vanadium 4-8 parts, Tungstic anhydride. 4-6 part, aluminium oxide 5-8 part, amorphous silica-alumina 4-8 part, molecular sieve 6-7 part.
Described Zinc oxide particles mean particle diameter is 23nm, and the mean particle diameter of manganese oxide particle is 40nm.
Aluminium oxide is selected from boehmite, gibbsite, boehmite, γ-aluminium oxide, α-aluminium oxide, δ-oxidation
Aluminum, θ-aluminium oxide or their mixture.
Described molecular sieve is the mixture of zsm-5, beta-zeolite molecular sieve and mfi molecular sieve, and mass ratio is 1-2:3-6:
2-5.
The preparation method of above-mentioned catalyst comprises the steps:
1), by above-mentioned stannum oxide 7-10 part, Zinc oxide particles 5-10 part, basic aluminum sulfate 4-6 part, manganese oxide particle 4-10 part,
3 parts of tungsten oxide, cocoanut active charcoal 5-8 part, attapulgite modified 4-8 part, vanadic anhydride 4-8 part, Tungstic anhydride. 4-6 part, oxygen
Change aluminum 5-8 part, amorphous silica-alumina 4-8 part, molecular sieve 6-7 part mix homogeneously, compressing, obtain catalyst carrier.
Described amorphous silica-alumina comprises silicon oxide 8wt%-50wt%, and specific surface area is 700-800m2/ g, pore volume is
1.6-1.8ml/g, bore dia 8-15nm, shared pore volume accounts for the 95%- 98% of total pore volume, and infrared total acid content is 0.30-
0.45mmol/g, middle strong acid amount/infrared total acid content is that 0.56-0.81, l acid amount/b acid is measured as 1.40-2.30.
2), adopt dipping solution impregnated catalyst support, through in hermetic container situ crystallization, being dried to obtain catalysis
Agent presoma.
The preparation process of dipping solution is as follows, weighs molybdenum oxide and basic nickel carbonate, plus deionized water mix homogeneously, adds
Concentration is 85% phosphoric acid, is heated to 75 DEG C, and constant temperature one hour obtains bottle green clear transparent solutions, adds ammonium metatungstate
Stirring, obtains final product impregnation liquid after dissolving.
The reaction temperature of in-situ crystallization reaction is 35-80 DEG C, and the response time is 2-8 hour.
Baking temperature is 230-250 degree Celsius, vacuum drying, and vacuum is 0.8mpa.
3), catalyst precursor in step 2 is added in plasma generator, the power of adjustment plasma generator
Plasma-activated for carrying out during 800-1000w, and plasma activation time is 30-40min, prepared catalyst.
The cavity of plasma generator is metallic cavity or glass chamber；Exciting electrode is low frequency electrode, radio-frequency electrode
Or microwave electrodes.
When described catalyst precursor is inserted described plasma generator, first hydrogenation catalyst is evenly placed upon
In the good container of electric conductivity, container is placed in plasma generator, opens vacuum pump, in plasma generator
Form the vacuum of 10-50pa in vacuum cavity.
Claims (6)
1. a kind of preparation method of isobutene. it is characterised in that: comprise the steps: raw material iso-butane and hydrogen, vapor
Form gaseous mixture, wherein iso-butane: hydrogen: the mol ratio of vapor is 1: 0.2-0.3:4-6 after mixing；
Reaction temperature 800-1000 DEG C, pressure 2-5mpa, gaseous mixture volume space velocity is 100-1000 hour-1, gaseous mixture enters solid
Fixed bed reactor, contacts with adding dehydrogenation in fixed bed reactors, obtains isobutene.；
Above-mentioned catalyst is by the material composition of following weight portion, stannum oxide 7-10 part, Zinc oxide particles 5-10 part, basic aluminum sulfate
4-6 part, manganese oxide particle 4-10 part, 3 parts of tungsten oxide, cocoanut active charcoal 5-8 part, attapulgite modified 4-8 part, five oxidations two
Vanadium 4-8 part, Tungstic anhydride. 4-6 part, aluminium oxide 5-8 part, amorphous silica-alumina 4-8 part, molecular sieve 6-7 part.
2. isobutene. according to claim 1 preparation method it is characterised in that: described Zinc oxide particles averaged particles are straight
Footpath is 23nm；
The mean particle diameter of manganese oxide particle is 40nm.
3. isobutene. according to claim 1 preparation method it is characterised in that: aluminium oxide be selected from boehmite, three
Diaspore, boehmite, γ-aluminium oxide, α-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide or their mixture.
4. isobutene. according to claim 1 preparation method it is characterised in that: described molecular sieve be zsm-5, β zeolite
Molecular sieve and the mixture of mfi molecular sieve, mass ratio is 1-2:3-6:2-5.
5. isobutene. according to claim 1 preparation method it is characterised in that: the preparation method of above-mentioned catalyst is such as
Under:
1), by above-mentioned stannum oxide 7-10 part, Zinc oxide particles 5-10 part, basic aluminum sulfate 4-6 part, manganese oxide particle 4-10 part,
3 parts of tungsten oxide, cocoanut active charcoal 5-8 part, attapulgite modified 4-8 part, vanadic anhydride 4-8 part, Tungstic anhydride. 4-6 part, oxygen
Change aluminum 5-8 part, amorphous silica-alumina 4-8 part, molecular sieve 6-7 part mix homogeneously, compressing, obtain catalyst carrier；
2), adopt dipping solution impregnated catalyst support, through in hermetic container situ crystallization, before being dried to obtain catalyst
Drive body；
The reaction temperature of in-situ crystallization reaction is 35-80 DEG C, and the response time is 2-8 hour；Baking temperature is that 230-250 is Celsius
Degree, vacuum drying, vacuum is 0.8mpa, 3), by step 2) in catalyst precursor add in plasma generator, adjustment
The power of plasma generator is plasma-activated for carrying out during 800-1000w, and plasma activation time is 30-
40min, prepared catalyst.
6. isobutene. according to claim 5 preparation method it is characterised in that: the preparation process of dipping solution is as follows,
Weigh molybdenum oxide and basic nickel carbonate, plus deionized water mix homogeneously, the phosphoric acid adding concentration to be 85%, it is heated to 75 DEG C, permanent
Temperature one hour, obtains bottle green clear transparent solutions, adds ammonium metatungstate stirring, obtains final product impregnation liquid after dissolving.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610735050.3A CN106365939A (en) | 2016-08-28 | 2016-08-28 | Method for preparing isobutene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610735050.3A CN106365939A (en) | 2016-08-28 | 2016-08-28 | Method for preparing isobutene |
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| CN106365939A true CN106365939A (en) | 2017-02-01 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503503A (en) * | 2017-02-28 | 2018-09-07 | 中国石油化工股份有限公司 | A kind of method that catalytic dehydrogenation of isobutane prepares isobutene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1592654A (en) * | 2000-10-17 | 2005-03-09 | 巴斯福股份公司 | Catalyst comprising a support and a catalytically active oxide material applied to the surface of the substrate |
| CN103420768A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing isobutene from isobutane |
| CN103998126A (en) * | 2011-12-22 | 2014-08-20 | 沙特基础工业公司 | Zinc and/or manganese aluminate catalyst useful for alkane dehdyrogenation |
-
2016
- 2016-08-28 CN CN201610735050.3A patent/CN106365939A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1592654A (en) * | 2000-10-17 | 2005-03-09 | 巴斯福股份公司 | Catalyst comprising a support and a catalytically active oxide material applied to the surface of the substrate |
| CN103998126A (en) * | 2011-12-22 | 2014-08-20 | 沙特基础工业公司 | Zinc and/or manganese aluminate catalyst useful for alkane dehdyrogenation |
| CN103420768A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing isobutene from isobutane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503503A (en) * | 2017-02-28 | 2018-09-07 | 中国石油化工股份有限公司 | A kind of method that catalytic dehydrogenation of isobutane prepares isobutene |
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