CN106622302A - Preparation method of catalyst for preparation of high-purity olefin - Google Patents
Preparation method of catalyst for preparation of high-purity olefin Download PDFInfo
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- CN106622302A CN106622302A CN201611067959.2A CN201611067959A CN106622302A CN 106622302 A CN106622302 A CN 106622302A CN 201611067959 A CN201611067959 A CN 201611067959A CN 106622302 A CN106622302 A CN 106622302A
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- catalyst
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- etherate
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
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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
The invention discloses a preparation method of an efficient etherate cracking catalyst. The catalyst can be applied to preparation of a high-purity olefin. According to the efficient etherate cracking catalyst, a high-activity TiO2-X2O3-SO4<2->/Al2O3 type catalyst is prepared by loading active components with modified activated alumina balls. The preparation method comprises the following steps of adding the modified activated alumina balls into a solution containing Ti(SO4)2 and X2O3, dipping, filtering, drying and calcining to prepare the high-activity TiO2-X2O3-SO4<2->/Al2O3 type catalyst.
Description
Technical field
The invention mainly relates to a kind of efficient etherate cracking prepares the method for preparing catalyst of alkene.The catalyst be by
Titanium oxide, sulfate radical and rare earth oxide are supported on the multicomponent TiO on modified alumina carrier2-X2O3-SO4 2-/
Al2O3Type catalyst.
Background technology
Alkene is important fine-chemical intermediate raw material, and highly purified alkene is applied not only to manufacture gasoline and lubricating oil adds
Plus agent, but also can be with the centre for opening manufacture agricultural chemicals, coating, antioxidant, essence, synthetic rubber, resin and organic synthesis
Body.Therefore, Jing in decades, its social required quantity all the time rapidly increasing, with expanding economy, in following 10 years it
Demand will constantly rise.
Production alkene main method have sulfuric acid extraction, oil gas separate, tert-pentyl alcohol dehydration, diolefin hydrogenation, penta
Alkane dehydrogenation and TAME ether solutions.It is the main method for industrially producing isoalkene that etherate cracking prepares isoalkene, and traditional
Method is compared, with product purity is high, reaction condition it is relative relax, high income the features such as be used widely.
Catalyst is the key that ether solution prepares alkene, and the performance of catalyst directly influences the conversion of ether cracking reaction
The important indicators such as rate, selectivity of product.
From the point of view of reaction in itself, etherate cracking is the endothermic reaction, improves reaction temperature and is conducive to the life of alkene, temperature compared with
Gao Shi, etherate can substantially completely decompose, and be avoided that etherate separation and recovery is recycled, and reduce cost.But temperature is raised, and is had
Some side reactions occur, and such as olefin(e) oligomerization causes the loss of alkene, methanol dehydration to generate dimethyl ether, and the generation of dimethyl ether can be reduced
The rate of recovery of methyl alcohol, can result in the need for adding again a large amount of methyl alcohol in etherification reaction system, while excessive dimethyl ether is increased
Subsequent products detached costs；The water that dimethyl ether is produced when generating also is lost product with alkene hydration, while by-product
The generation of the thing tertiary alcohol increased cost etc. to the separation and purification of product.Current catalyst system is mainly：Alumina system, oxygen
SiClx system, ion exchange resin system, sulfate system, molecular sieve system, heteropolyacid system.But they are more or less present
Some problems：The shortcoming of ion-exchange resin catalyst is that resistance to elevated temperatures is poor, when the temperature of reaction is too high, activity therein
Easily decomposition comes off component, and due to being limited by reaction temperature, the conversion ratio of reaction is all relatively low.Heteropolyacid system catalyst
Have the disadvantage that air speed is low during etherate cracking reaction, production efficiency is low, and reaction temperature is higher, and energy consumption is big.Fluoride system is urged
Agent compares relatively low to the conversion ratio of TAME.
Therefore provide a kind of under relatively low reaction temperature, there is high conversion ratio and selective efficiently etherate cracking system
The preparation method of the catalyst of standby alkene be related industry department it is highly desirable.
The content of the invention
Etherate cracking is the back reaction of etherate synthetic reaction, under catalyst action, is cracked into alkene and methyl alcohol.With
Tert amyl methyl ether(TAME) is generated as a example by isoamyl alkene reaction：
It may also happen that following main side reaction when tert amyl methyl ether(TAME) is cracked：
1. the oligomerisation reaction of iso-amylene
2. Dehydration of methanol
3. the hydration reaction of iso-amylene
Above-mentioned reaction is all that the growing amount of reversible reaction, tert amyl methyl ether(TAME) cracking conversion ratio and accessory substance has close with reaction temperature
The relation cut, improving reaction temperature can increase the equilibrium constant of main reaction, improve the conversion ratio of tert amyl methyl ether(TAME), but while
Also the generation of side reaction is accelerated, in order to improve the selectivity of main reaction thing iso-amylene and methyl alcohol, suppresses the generation of side reaction, such as
Fruit decomposition of methyl tert-amyl ether under relatively low reaction temperature prepares iso-amylene, and above-mentioned side reaction just can be effectively suppressed,
Some reactions even no longer occur, to ensure having high iso-amylene and methanol selectivity, while the activity of catalyst is improved, to protect
Card has high TAME cracking conversion ratios and reaction velocity.Etherate cracking situation is all similar to.
It is therefore an object of the present invention to the premise of the high conversion in the high selectivity and etherate for ensureing methyl alcohol and alkene
Under, there is provided one kind in the case where other process conditions are basically unchanged, reaction temperature can be reduced, the volume space velocity of etherate into
Improve again, prepare high activated catalyst simple, with low cost.
The present invention proposes a kind of preparation method of efficient etherate catalyst for cracking, it is characterised in that select modified active
Alumina support adopts infusion process load active component, and Jing is filtered, is dried, roasting, finally gives TiO2-X2O3-SO4 2-/Al2O3
Type catalyst.
Modified aluminium oxide supports of the present invention are that particle diameter is 2-5mm, and purity is the commercially available active oxidation of 90%-99%
Aluminium, can be α-Al2O3、β-Al2O3、γ-Al2O3Or θ-Al2O3In one kind, it is modified and obtain.
The ether catalyst for cracking is obtained by infusion process load active component.Preparation method is as follows：Modified work
Property alumina balls impregnated in Ti (SO4)2With contain X2O3In solution, wherein X2O3For rare earth or metal oxide, from rare earth
One kind of the soluble-salt of the metals such as Elements C e, La, Sm and Zr；Ti(SO4)2Solution concentration is 0.01mol/L-10 mol/L,
X2O3Concentration of aqueous solution is 0.01mol/L-10mol/L, after 1 ~ 8h of dipping, is filtered, filter cake in 100 ~ 15 DEG C of 2 ~ 8h of drying, then
TiO is obtained in 300 ~ 800 DEG C of 1 ~ 6h of roasting2-X2O3-SO4 2-/Al2O3Type catalyst.
Etherate catalyst for cracking activity rating process according to the present invention is in homemade micro fixed-bed reactor
Carry out, etherificate raw material is contacted and reacted with above-mentioned catalyst under certain condition.Being etherified the purity of raw material is
98%-99%, impurity is methyl alcohol, alkene, the tertiary alcohol.Reaction pressure is normal pressure, and reaction temperature is 100 ~ 300 DEG C, and liquid air speed is 0.1
~20h-1；Optimum process condition is：Normal pressure, reaction temperature is 120 ~ 220 DEG C, and liquid air speed is 1 ~ 15 h-1。
Etherate prepared by the present invention is cracked to form the active height of catalyst of high purity olefin, selective good, stable
The characteristics of property is excellent, and catalyst preparation low cost, easy industrialization simple to operate.
Specific embodiment
The following examples further will be described to the present invention, but be in no way intended to limit the scope of the present invention.
Embodiment 1
By the Al of modified mistake2O3Ball is immersed in the Ti (SO of the 0.02mol/L of 100ml4)2With the Ce of 0.05mol/L2(SO4)3Dipping
In solution, 3h is dried in 120 DEG C of baking ovens, the roasting 3h at 400 DEG C obtains the TiO that the present invention prepares efficient alkene2-Ce2O3-
SO4 2-/Al2O3Type catalyst.
12g catalyst is fitted into the fixed bed reactors of Φ=16mm diameters, methyl tertiary butyl ether(MTBE) micro-amounts of liquids sample introduction
Pump feeds, and controls liquid air speed for 3h-1, reaction temperature is 130 DEG C, and methyl tertiary butyl ether(MTBE) conversion ratio is 90.1%, and isobutene is selected
Property is 100%, and methanol selectivity is 99.8%.
12g catalyst is fitted into the fixed bed reactors of Φ=16mm diameters, tert amyl methyl ether(TAME) micro-amounts of liquids sample introduction
Pump feeds, and controls liquid air speed for 4h-1, reaction temperature is 160 DEG C, and tert amyl methyl ether(TAME) conversion ratio is 98.1%, and iso-amylene is selected
Property is 100%, and methanol selectivity is 99.5%.
Embodiment 2
By the Al of modified mistake2O3Ball is immersed in the Ti (SO of the 2.0mol/L of 100ml4)2With the La (NO of 0.6mol/L3)3Dipping is molten
In liquid, 3h is dried in 120 DEG C of baking ovens, the roasting 3h at 400 DEG C obtains the TiO that the present invention prepares efficient alkene2-La2O3-
SO4 2-/Al2O3Type catalyst.
12g catalyst is fitted into the fixed bed reactors of Φ=16mm diameters, methyl tertiary butyl ether(MTBE) micro-amounts of liquids sample introduction
Pump feeds, and controls liquid air speed for 5h-1, reaction temperature is 170 DEG C, and methyl tertiary butyl ether(MTBE) conversion ratio is 99.1%, and isobutene is selected
Property is 99.9%, and methanol selectivity is 99.3%.
12g catalyst is fitted into the fixed bed reactors of Φ=16mm diameters, tert amyl methyl ether(TAME) micro-amounts of liquids sample introduction
Pump feeds, and controls liquid air speed for 12h-1, reaction temperature is 180 DEG C, and tert amyl methyl ether(TAME) conversion ratio is 98.2%, iso-amylene choosing
Selecting property is 100%, and methanol selectivity is 99.4%.
Embodiment 3
By the Al of modified mistake2O3Ball is immersed in the Ti (SO of the 6.0mol/L of 100ml4)2With the Sm (NO of 4.0mol/L3)3Dipping is molten
In liquid, 2h is dried in 120 DEG C of baking ovens, the roasting 3h at 600 DEG C obtains the TiO that the present invention prepares efficient alkene2-Sm2O3-
SO4 2-/Al2O3Type catalyst.
12g catalyst is fitted into the fixed bed reactors of Φ=16mm diameters, tert amyl methyl ether(TAME) micro-amounts of liquids sample introduction
Pump feeds, and controls liquid air speed for 15h-1, reaction temperature is 190 DEG C, and tert amyl methyl ether(TAME) conversion ratio is 99.8%, iso-amylene choosing
Selecting property is 100%, and methanol selectivity is 99.2%.
Embodiment 4
By the Al of modified mistake2O3Ball is immersed in the Ti (SO of the 8.0mol/L of 100ml4)2With the Zr (NO of 1.5mol/L3)3Dipping is molten
In liquid, 6h is dried in 130 DEG C of baking ovens, the roasting 3h at 700 DEG C obtains the TiO that the present invention prepares efficient alkene2-Zr2O3-
SO4 2-/Al2O3Type catalyst.
12g catalyst is fitted into the fixed bed reactors of Φ=16mm diameters, methyl tertiary butyl ether(MTBE) micro-amounts of liquids sample introduction
Pump feeds, and controls liquid air speed for 8h-1, reaction temperature is 200 DEG C, and methyl tertiary butyl ether(MTBE) conversion ratio is 99.8%, and iso-amylene is selected
Property is 98.8%, and methanol selectivity is 92.5%.
Claims (4)
1. a kind of preparation method for preparing etherate catalyst for cracking, its feature includes：Modified activated alumina ball warp dipping
It is dried after method load active component, roasting is obtained highly active TiO2-X2O3-SO4 2-/Al2O3Type catalyst.
2. according to claim 1 methods described, it is characterised in that described modified active oxidation aluminium ball is that particle diameter is 2-5mm,
Purity is the commercially available activated alumina of 90%-99%, can be α-Al2O3、β-Al2O3、γ-Al2O3Or θ-Al2O3In a kind of Jing
It is modified and is obtained.
3. according to claim 1 methods described, it is characterised in that described infusion process is by above-mentioned modified activated alumina
Ball impregnated in Ti (SO4)2With contain X2O3In solution, wherein X2O3For rare earth or metal oxide, from rare earth element ce,
One kind of the soluble-salt of the metals such as La, Sm and Zr；Ti(SO4)2Solution concentration is 0.01mol/L-10 mol/L, X2O3It is water-soluble
Liquid concentration is 0.01mol/L-10mol/L, after 1 ~ 8h of dipping, is filtered, filter cake in 100 ~ 15 DEG C of 2 ~ 8h of drying, then 300 ~
800 DEG C of 1 ~ 6h of roasting obtain TiO2-X2O3-SO4 2-/Al2O3Type catalyst.
4. the catalyst described in claim 1 is used for the reaction that ether-splitting solution prepares alkene, it is characterised in that in fixed bed reactors
It is middle by etherate under the following conditions, contact with catalyst and react, reaction pressure is normal pressure, reaction temperature is 100 ~
300 DEG C, liquid air speed is 0.1 ~ 20h-1；Optimum process condition is：Normal pressure, reaction temperature be 120 ~ 220 DEG C, liquid air speed be 1 ~
15 h-1。
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| CN201611067959.2A CN106622302A (en) | 2016-11-29 | 2016-11-29 | Preparation method of catalyst for preparation of high-purity olefin |
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| CN201611067959.2A CN106622302A (en) | 2016-11-29 | 2016-11-29 | Preparation method of catalyst for preparation of high-purity olefin |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152476A (en) * | 1995-12-19 | 1997-06-25 | 南开大学 | Catalyst for preparing methyl tert-butyl ether |
| CN1418729A (en) * | 2002-12-06 | 2003-05-21 | 华东理工大学 | Catalyst for producing isobutene by cracking methyl tert-butyl ether |
| CN1425500A (en) * | 2002-12-31 | 2003-06-25 | 曲阜师范大学 | Granular solid super strong acid catalyst and its preparing method |
| CN1680028A (en) * | 2005-01-31 | 2005-10-12 | 南京工业大学 | Solid superstrong acid catalyst of esterification of preparation thereof |
| CN101558076A (en) * | 2006-10-25 | 2009-10-14 | 玛特科国际有限公司 | Process for the preparation of sucrose-6-ester by esterification in the presence of solid superacid catalyst |
| CN103041834A (en) * | 2013-01-18 | 2013-04-17 | 华东理工大学 | Catalyst for preparing isoamylene by splitting decomposition of t-amyl-methyl ether and preparation method and application thereof |
| CN106031876A (en) * | 2015-03-19 | 2016-10-19 | 华东理工大学 | Catalyst for preparing isobutene by cracking of ether and preparation method thereof |
-
2016
- 2016-11-29 CN CN201611067959.2A patent/CN106622302A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152476A (en) * | 1995-12-19 | 1997-06-25 | 南开大学 | Catalyst for preparing methyl tert-butyl ether |
| CN1418729A (en) * | 2002-12-06 | 2003-05-21 | 华东理工大学 | Catalyst for producing isobutene by cracking methyl tert-butyl ether |
| CN1425500A (en) * | 2002-12-31 | 2003-06-25 | 曲阜师范大学 | Granular solid super strong acid catalyst and its preparing method |
| CN1680028A (en) * | 2005-01-31 | 2005-10-12 | 南京工业大学 | Solid superstrong acid catalyst of esterification of preparation thereof |
| CN101558076A (en) * | 2006-10-25 | 2009-10-14 | 玛特科国际有限公司 | Process for the preparation of sucrose-6-ester by esterification in the presence of solid superacid catalyst |
| CN103041834A (en) * | 2013-01-18 | 2013-04-17 | 华东理工大学 | Catalyst for preparing isoamylene by splitting decomposition of t-amyl-methyl ether and preparation method and application thereof |
| CN106031876A (en) * | 2015-03-19 | 2016-10-19 | 华东理工大学 | Catalyst for preparing isobutene by cracking of ether and preparation method thereof |
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Application publication date: 20170510 |