CN106348995A - Preparation method of high-purity isobutene - Google Patents
Preparation method of high-purity isobutene Download PDFInfo
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- CN106348995A CN106348995A CN201610735057.5A CN201610735057A CN106348995A CN 106348995 A CN106348995 A CN 106348995A CN 201610735057 A CN201610735057 A CN 201610735057A CN 106348995 A CN106348995 A CN 106348995A
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- isobutene
- molecular sieve
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- hydrogen
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of high-purity isobutene. The preparation method includes: mixing raw materials of isobutene with hydrogen and steamed water for form a gas mixture and allowing the gas mixture to enter a fixed bed reactor to contact with an added dehydrogenation catalyst in the fixed bed reactor to obtain an intermediate product; performing gas-liquid separation on the intermediate product with pressure ranging from 0.8MPa to 1.0MPa at the temperature of 20-30DEG C, performing adsorption on separated gas phase by adopting transformation adsorption device filled with an adsorbing agent, and separating the hydrogen from isobutene and isobutylene components to obtain isobutene with the purity of 99.7%. By the above mode, conversion rate of isobutene can reach 99.9%, selectivity of isobutene is increased by 50%, the purity of the prepared isobutene can reach 99.7%, pollution is avoided, and energy consumption is decreased 10-20% as compared to that with a traditional production method.
Description
Technical field
The present invention relates to chemical industry synthesis field, more particularly, to a kind of side preparing high-purity isobutylene 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.
There is the isobutene. that iso-butane conversion ratio is low, selective isobutene is poor, prepare in the preparation method of existing isobutene.
Purity is low, the shortcomings of high energy consumption, equipment investment are 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 high conversion rate, and isobutene. selects
Selecting property is high, and the isobutene. purity of preparation is high, and energy consumption is low, equipment investment
Little, the preparation method of the high-purity isobutylene of environmentally safe.
The present invention employs the following technical solutions: a kind of preparation method of high-purity isobutylene it is characterised in that: include as follows
Step:
A, raw material iso-butane is mixed with hydrogen, vapor after formed gaseous mixture, wherein iso-butane: hydrogen: vapor mole
Than for 1: 0.2-0.3:4-6；
Gaseous mixture enters fixed bed reactors, contacts and reacts with adding dehydrogenation in fixed bed reactors, obtains middle product
Thing；
Reaction temperature 800-1000 DEG C, pressure 2-5mpa, gaseous mixture volume space velocity is 100-1000 hour-1；
B, intermediate product is 0.8-1.0mpa in pressure, under the conditions of temperature is 20-30 DEG C, carries out gas-liquid separation, after separating
Through being adsorbed using the pressure-swing absorption apparatus equipped with adsorbent, adsorptive pressure is 2-3.5mpa to gas phase, and temperature is 70-90 DEG C,
Hydrogen in gas phase and iso-butane, isobutyl olefinic constituent are carried out separate, obtain, after separating, the isobutene. that purity is 99.7%.
The following is further improvement of the present invention:
Described adsorbent is y type molecular sieve, the mixture of β zeolite, zsm -2 molecular sieve and sapo -11 molecular sieve；
Described y type molecular sieve, the mass ratio of β zeolite, zsm-5 molecular sieve and sapo-11 molecular sieve are 8:5:3:2.
Improve further:
The relative crystallinity of described sapo-11 molecular sieve is 98%, and crystal particle diameter is 2.5 μm.
Improve further:
The relative crystallinity 95%- 110% of described y type molecular sieve, crystal particle diameter is 1.8 μm.
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 the isobutene. purity of preparation is up to 99.7%, pollution-free, and the more traditional production method of energy consumption reduces 10-20%,
Equipment investment reduces by 10-40%.
Specific embodiment
Embodiment, a kind of preparation method of high-purity isobutylene, comprise the steps:
A, raw material iso-butane is mixed with hydrogen, vapor after formed gaseous mixture, wherein iso-butane: hydrogen: vapor mole
Than for 1: 0.2-0.3:4-6；
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 intermediate product；
B, intermediate product is 0.8-1.0mpa in pressure, under the conditions of temperature is 20-30 DEG C, carries out gas-liquid separation, after separating
Through being adsorbed using the pressure-swing absorption apparatus equipped with adsorbent, adsorptive pressure is 2-3.5mpa to gas phase, and temperature is 70-90 DEG C,
Hydrogen in gas phase and iso-butane, isobutyl olefinic constituent are carried out separate, obtain, after separating, the isobutene. that purity is 99.7%.
Described adsorbent is y type molecular sieve, the mixture of β zeolite, zsm -2 molecular sieve and sapo -11 molecular sieve；
Described y type molecular sieve, the mass ratio of β zeolite, zsm-5 molecular sieve and sapo-11 molecular sieve are 8:5:3:2.
The relative crystallinity of described sapo-11 molecular sieve is 98%, and crystal particle diameter is 2.5 μm.
The relative crystallinity 95%～110% of described y type molecular sieve, crystal particle diameter is 1.8 μm.
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 DEG C, 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 (4)
1. a kind of preparation method of high-purity isobutylene it is characterised in that: comprise the steps:
A, raw material iso-butane is mixed with hydrogen, vapor after formed gaseous mixture, wherein iso-butane: hydrogen: vapor mole
Than for 1: 0.2-0.3:4-6；
Gaseous mixture enters fixed bed reactors, contacts and reacts with adding dehydrogenation in fixed bed reactors, obtains middle product
Thing；
Reaction temperature 800-1000 DEG C, pressure 2-5mpa, gaseous mixture volume space velocity is 100-1000 hour-1；
B, intermediate product is 0.8-1.0mpa in pressure, under the conditions of temperature is 20-30 DEG C, carries out gas-liquid separation, after separating
Through being adsorbed using the pressure-swing absorption apparatus equipped with adsorbent, adsorptive pressure is 2-3.5mpa to gas phase, and temperature is 70-90 DEG C,
Hydrogen in gas phase and iso-butane, isobutyl olefinic constituent are carried out separate, obtain, after separating, the isobutene. that purity is 99.7%.
2. high-purity isobutylene according to claim 1 preparation method it is characterised in that: described adsorbent divides for y type
Son sieve, the mixture of β zeolite, zsm -2 molecular sieve and sapo -11 molecular sieve；
Described y type molecular sieve, the mass ratio of β zeolite, zsm-5 molecular sieve and sapo-11 molecular sieve are 8:5:3:2.
3. high-purity isobutylene according to claim 2 preparation method it is characterised in that: described sapo-11 molecular sieve
Relative crystallinity be 98%, crystal particle diameter be 2.5 μm.
4. high-purity isobutylene according to claim 3 preparation method it is characterised in that: the phase of described y type molecular sieve
To degree of crystallinity 95%-110%, crystal particle diameter is 1.8 μm.
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| CN201610735057.5A CN106348995A (en) | 2016-08-28 | 2016-08-28 | Preparation method of high-purity isobutene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044180A (en) * | 2012-12-28 | 2013-04-17 | 北京石油化工学院 | Method for preparing isobutylene by dehydrogenizing iso-butane |
| 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 |
| CN103420338A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Hydrogen gas separation method for isobutane dehydrogenation reaction gas |
| CN103664455A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of propylene |
-
2016
- 2016-08-28 CN CN201610735057.5A patent/CN106348995A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103420338A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Hydrogen gas separation method for isobutane dehydrogenation reaction gas |
| CN103664455A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of propylene |
| CN103044180A (en) * | 2012-12-28 | 2013-04-17 | 北京石油化工学院 | Method for preparing isobutylene by dehydrogenizing iso-butane |
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Application publication date: 20170125 |