CN106607067B - Olefin disproportionation catalyst - Google Patents
Olefin disproportionation catalyst Download PDFInfo
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- CN106607067B CN106607067B CN201510686241.0A CN201510686241A CN106607067B CN 106607067 B CN106607067 B CN 106607067B CN 201510686241 A CN201510686241 A CN 201510686241A CN 106607067 B CN106607067 B CN 106607067B
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Abstract
The present invention relates to a kind of olefin disproportionation catalysts, mainly solve the problems, such as that catalyst disproportionation activity existing in the prior art is low.The present invention is by using a kind of olefin disproportionation catalyst, based on parts by weight, including following components: a) 0.01~10 part of P elements or its oxide；B) 1~20 part of rhenium element or its oxide；C) technical solution of 60~99 parts of aluminium oxide, preferably solves the problems, such as this, can be used in the industrial production of olefin dismutation reaction.
Description
Technical field
The present invention relates to a kind of olefin disproportionation catalysts.
Technical background
Olefin dismutation reaction is also known as metathesis reaction or metathesis reaction, is that original C=C key is disconnected between two reaction olefin hydrocarbon molecules
Split, recombinate generate have new C=C double bond olefin hydrocarbon molecules process, using olefin dismutation reaction can by it is some it is relatively inexpensive,
Olefin feedstock abundant is converted into the higher olefin product of a variety of added values.It can indicate that olefin(e) disproportionation is anti-with following reaction equation
Answer process:
R in reaction equation1, R2, R3, R4Respectively represent different alkyl or hydrogen atom.Wherein if same alkene
Disproportionated reaction (such as formula 1) is known as itself disproportionation (self-metathesis)；And the disproportionated reaction (formula 2) between different alkene
Then it is known as cross disproportionation (cross-metathesis).
Acted on using the cross disproportionation of amylene and ethylene, can by the way that appropriate ethylene is added, by relative surplus, added value compared with
Low C5Olefin feedstock is converted into high added value propylene product.
Olefin dismutation reaction is in VIB、VIIB, carry out under metallic compound catalytic action in VIII, olefin(e) disproportionation is urged
Agent can be homogeneous catalyst and heterogeneous catalyst, the oxide or metal that wherein heterogeneous catalyst is typically referred to Re, Mo or W
The form of organic coordination compound is carried on SiO2、Al2O3、Al2O3-SiO2Equal high-ratio surfaces supported catalyst.Due to active gold
The difference of the factors such as category, support, carried metal species and carrier function so that catalyst shown in disproportionated reaction compared with
Big performance difference.
US6271430 discloses a kind of disproportionation by 1- butylene and 2- butylene and obtains the technique of propylene and amylene.
The catalyst that the technique uses is Re2O7/Al2O3.Using liquid and solid phase reaction, reaction increases with the time, conversion ratio and selectivity
All decline.US6166279 uses identical Re2O7/Al2O3Catalyst, reactor are moving bed, while using ethylene and amylene
Two reactors are reacted, there are certain difficulties for the catalyst regeneration.
US3767565 discloses a kind of method for improving fuel octane number, wherein including WO3/SiO2With the catalysis of MgO
By the C of olefinic fuel in agent5Fraction is reacted with ethylene, ethylene, propylene, n- butylene and isobutene is formed, by gained propylene
It is disproportionated, then gained n- butylene is alkylated with iso-butane.
CN1490289A discloses a kind of method of preparing propylene by butene disproportionation, uses with SiO2For carrier, WO is loaded3Consolidate
Bed catalyst, and specific surface area of catalyst is 270~550 meters2/ gram, 250~450 DEG C of reaction temperature, reaction pressure 0~
10MPa, liquid phase air speed 0.1~1.0 hour-1Under the conditions of occur disproportionated reaction generate propylene.
CN1228404A discloses the preparation of propylene and 1- butylene if necessary, comprising: a) in Section VIb、VIIbOr
In the presence of at least one displacement catalyst of VIII group transition metal, makes 1- butylene and 2- butene reaction, generate propylene and 2- penta
Alkene；B) then separation product；C) again with step a) in the presence of identical catalyst, make the 2- amylene and ethylene reaction, generate third
Alkene and 1- butylene；D) then separation product；E) it releases and is at least partly formed by 1- butylene, and/or deposited in isomerization catalyst
Make to be formed by at least partly isomerization of 1- butylene under, obtain 2- butylene, will then the 1- butylene being not bled off and be formed by
2- butylene and a) the unreacted C in part in step4Fraction return step a) together.
CN102614867A discloses one kind while having mesoporous and macropore combined porous structure olefin(e) disproportionation catalyst,
Including selected from rhenium, molybdenum, tungsten at least one of oxide catalytically-active metals and catalyst carrier, the catalyst carrier be
Aluminium oxide with mesopore/macropore combined cellular structure, the mesoporous aperture are 2~25nm, and the aperture of the macropore is 50
~5000nm；Specific surface area is greater than 200m20.6~1.8cm of/g, Kong Rongwei3/ g, intermediary hole account for the 40%~90% of total pore volume,
Macropore accounts for the 10%~60% of total pore volume, macropore through hole window or mesoporous is connected.The catalyst carrier containing calorize by closing
Object and the mixing of mesoporous template and macroporous granules template are roasted and are prepared.Above-mentioned catalyst solves conventional art
There is a problem of that catalyst activity is low, inactivation is very fast in middle low-carbon alkene disproportionation.Also disclose the olefin(e) disproportionation catalyst
Preparation method.
CN101172925A discloses the method for a kind of ethylene and producing propene from butylene by disproportion.Using ethylene, butylene as raw material,
The weight ratio of ethylene and butylene is 0.1~3:1, and ethylene is contacted with catalyst 1 first with first strand of butylene, generates first burst of reaction
Effluent；After first strand of reaction effluent is mixed with second strand of butylene, contacted with catalyst 2 generate second strand containing propylene it is anti-
Answer effluent；Wherein catalyst 1 or catalyst 2 include SiO2Carrier and be loaded in thereon be calculated as 0.1 with vehicle weight~
30% tungsten oxide.
CN1611297A discloses a kind of catalyst for preparing propylene by butene disproportionation, and butene feedstock can be 1- butylene, 2-
Butylene and its mixture or c4 fraction from steam cracking device add copper in oxidation tungsten/silicon dioxide catalyst system
Or its oxide component, preferable technical effect is achieved, can be used in the industrial production of preparing propylene by butene disproportionation.
Above-mentioned document is mainly used in the disproportionated reaction of butylene and ethylene, there is catalyst activity and Propylene Selectivity is low
The problem of.
Summary of the invention
The technical problem to be solved by the present invention is to the low problems of catalyst disproportionation activity existing in the prior art, provide
A kind of new olefin disproportionation catalyst.When the catalyst is for amylene and ethylene disproportionation preparation of propene, there is catalyst disproportionation
The high advantage of activity.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of olefin disproportionation catalyst, with weight
Number meter, including following components: a) 0.01~10 part of P elements or its oxide；B) 1~20 part of rhenium element or its oxide；c)
60~99 parts of aluminium oxide.
In above-mentioned technical proposal, based on parts by weight, the preferred scope of P elements or its oxide is 0.1~8 part, phosphorus member
The most preferred range of element or its oxide is 1~5 part；The preferred scope of rhenium element or its oxide is 5~15 parts；Aluminium oxide
Preferred scope is 70~85 parts；Above-mentioned olefin disproportionation catalyst, based on parts by weight, further include 0.01~1 part magnesium elements or
Its oxide, preferred scope are 0.05~0.1 part；The olefin disproportionation catalyst is used for amylene and ethylene disproportionation system third
Alkene reaction, using amylene and ethylene as raw material, in 20~100 DEG C of reaction temperature, 0.1~1MPa of reaction pressure, amylene weight space velocity
0.5~6 hour-1, ethylene and amylene molar ratio (1~6): under the conditions of 1 reaction generate propylene；Wherein, the preferred model of reaction temperature
Enclosing is 35~70 DEG C, and reaction pressure preferred scope is 0.3~0.6MPa, and amylene weight space velocity preferred scope is 1~3 hour-1, second
The molar ratio preferred scope of alkene and amylene is (2~4): 1.
The preparation method of olefin disproportionation catalyst in the present invention, successively the following steps are included:
(1) to Al2O3Middle addition sesbania powder and aqueous solution of nitric acid, through kneading, molding, drying, 500~700 DEG C of roastings 2~8
After hour, catalyst carrier is made；(2) catalyst carrier is loaded into phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate, through dry
It is dry and 500~600 DEG C roast 2~6 hours, catalyst intermediate is made；(3) catalyst intermediate is loaded into ammonium perrhenate
Or the olefin disproportionation catalyst is made through dry and 500~600 DEG C roast 2~6 hours in perrhenic acid.
The content of oxide species is measured by Xray fluorescence spectrometer (XRF) in above-mentioned olefin disproportionation catalyst.By sample pressure
After sheetmolding, the characteristic spectral line intensity of atom is measured, on 4580 type XRF (Rigaku) of ZSX-100e so as to find out sample
The content of middle oxide species.
The present invention is by increasing the acid amount of catalyst and acid strength using phosphorus as the co-catalyst of olefin disproportionation catalyst
Add, while improving the reduction temperature of catalyst, to effectively increase the reactivity of olefin disproportionation catalyst, enhances and urge
The stability of agent.Catalyst of the present invention is used for amylene and the reaction of ethylene propylene, in reaction temperature 20~100
DEG C, 0.1~1MPa of reaction pressure, weight space velocity 0.5~6 hour-1, ethylene and amylene molar ratio (1~6): under the conditions of 1, penta
For alkene conversion ratio up to 99.8%, the molar selectivity of propylene and 1- butylene is respectively 50.7% and 49.1%, achieves preferable skill
Art effect.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
9.099 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.0014 gram of phosphoric acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-1 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Using amylene and ethylene as raw material, in 50 DEG C of reaction temperature, reaction pressure 0.6MPa, amylene weight space velocity 2 hours-1、
The molar ratio of ethylene and amylene carries out evaluating catalyst under the conditions of being 3:1, and reaction result is listed in table 1.
[embodiment 2]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.1 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 1.38 grams of phosphoric acid, are stood at room temperature
It is 24 hours, dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-2 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 3]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
9.09 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.014 gram of phosphoric acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-3 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 4]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.3 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 1.105 grams of phosphoric acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-4 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 5]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
9 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.138 gram of phosphoric acid, are stood at room temperature
It is 24 hours, dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-5 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 6]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.6 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.69 gram of phosphoric acid, are stood at room temperature
It is 24 hours, dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-6 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 7]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.799 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.414 gram of phosphoric acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -1 is made.
Above-mentioned catalyst intermediate -1 is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -2 is made.
Above-mentioned catalyst intermediate -2 is impregnated in 7.5 milliliters of aqueous solutions containing 0.0037 gram of magnesium nitrate, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-7 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 8]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.7 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.414 gram of phosphoric acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -1 is made.
Above-mentioned catalyst intermediate -1 is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -2 is made.
Above-mentioned catalyst intermediate -2 is impregnated in 7.5 milliliters of aqueous solutions containing 0.368 gram of magnesium nitrate, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-8 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 9]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.795 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.414 gram of phosphoric acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -1 is made.
Above-mentioned catalyst intermediate -1 is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -2 is made.
Above-mentioned catalyst intermediate -2 is impregnated in 7.5 milliliters of aqueous solutions containing 0.0184 gram of magnesium nitrate, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-9 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 10]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.79 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.414 gram of phosphoric acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -1 is made.
Above-mentioned catalyst intermediate -1 is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -2 is made.
Above-mentioned catalyst intermediate -2 is impregnated in 7.5 milliliters of aqueous solutions containing 0.037 gram of magnesium nitrate, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-10 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 11]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.999 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 1.243 grams of phosphoric acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -1 is made.
Above-mentioned catalyst intermediate -1 is impregnated in 7.5 milliliters of aqueous solutions containing 0.104 gram of perrhenic acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate -2 is made.
Above-mentioned catalyst intermediate -2 is impregnated in 7.5 milliliters of aqueous solutions containing 0.0024 gram of copper nitrate, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst SSL-11 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 12]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
7.2 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 1.105 grams of phosphoric acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 2.074 grams of perrhenic acid, is stood at room temperature
It is 24 hours, dry, 520 DEG C after roasting 4 hours, catalyst SSL-12 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 13]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.9 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.828 gram of phosphoric acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.519 gram of perrhenic acid, is stood at room temperature
It is 24 hours, dry, 520 DEG C after roasting 4 hours, catalyst SSL-13 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[embodiment 14]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
8.1 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.552 gram of phosphoric acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 1.556 grams of perrhenic acid, is stood at room temperature
It is 24 hours, dry, 520 DEG C after roasting 4 hours, catalyst SSL-14 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[comparative example 1]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
9.1 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, at room temperature
24 hours are stood, it is dry, 520 DEG C after roasting 4 hours, catalyst BJL-1 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[comparative example 2]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
7.5 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 2.209 grams of phosphoric acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 phosphoric acid, stands 24 at room temperature
Hour, it is dry, 520 DEG C after roasting 4 hours, catalyst BJL-2 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
[comparative example 3]
By 20 grams of Al2O3It is uniformly mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fills
It is extruded into 1 millimeter of diameter of cylinder after point kneading, after roasting 5 hours, 2~3 millimeters of long catalyst are made through drying, 600 DEG C
Carrier.
9 grams of said catalyst carriers are impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst intermediate is made.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solutions containing 0.0233 gram of zinc nitrate, it is quiet at room temperature
It sets 24 hours, it is dry, 520 DEG C after roasting 4 hours, catalyst BJL-3 is made.
The content of oxide species is measured to obtain by XRF in catalyst, is shown in Table 1.
Evaluating catalyst condition is same as Example 1, and reaction result is listed in table 1.
Table 1
[embodiment 15-18]
With the catalyst of embodiment 10, change evaluation condition, reaction result is listed in table 2.
Table 2
Claims (7)
1. a kind of olefin disproportionation catalyst, based on parts by weight, including following components:
A) 3~5 parts of P elements or its oxide；
B) 5~9 parts of rhenium elements or its oxide；
C) 60~99 parts of aluminium oxide.
2. olefin disproportionation catalyst according to claim 1, it is characterised in that the content of aluminium oxide is based on parts by weight
70~85 parts.
3. olefin disproportionation catalyst according to claim 1 or 2, it is characterised in that based on parts by weight further include 0.01~
1 part of magnesium elements or its oxide.
4. olefin disproportionation catalyst according to claim 3, it is characterised in that magnesium elements or its oxidation based on parts by weight
The content of object is 0.05~0.1 part.
5. the described in any item olefin disproportionation catalysts of Claims 1 to 4 are used for amylene and ethylene disproportionation preparation of propene, with
Amylene and ethylene are raw material, small in 20~100 DEG C of reaction temperature, 0.1~1MPa of reaction pressure, amylene weight space velocity 0.5~6
When-1, ethylene and amylene molar ratio (1~6): under the conditions of 1 reaction generate propylene.
6. the purposes of olefin disproportionation catalyst described in claim 5, which is characterized in that amylene and ethylene disproportionation preparation of propene
35~70 DEG C of reaction temperature, 0.3~0.6MPa of reaction pressure, amylene weight space velocity 1~3 hour-1, ethylene and amylene mole
Than for (2~4): 1.
7. the preparation method of olefin disproportionation catalyst described in claim 1, successively the following steps are included:
(1) to Al2O3Middle addition sesbania powder and aqueous solution of nitric acid roast 2~8 hours through kneading, molding, drying, 500~700 DEG C
Afterwards, catalyst carrier is made；
(2) catalyst carrier is loaded into phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate, through dry and 500~600 DEG C of roastings
2~6 hours, catalyst intermediate is made；
(3) catalyst intermediate is loaded into ammonium perrhenate or perrhenic acid, through dry and 500~600 DEG C roast 2~6 hours,
The olefin disproportionation catalyst is made.
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| CN102794170A (en) * | 2011-05-25 | 2012-11-28 | 中国石油天然气股份有限公司 | Preparation method of supported rhenium catalyst for preparing alpha-olefin by high-carbon olefin disproportionation |
| CN103801347A (en) * | 2012-11-12 | 2014-05-21 | 中国科学院大连化学物理研究所 | Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst |
| CN104549232A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Rhenium-based disproportionation catalyst |
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| CN102794170A (en) * | 2011-05-25 | 2012-11-28 | 中国石油天然气股份有限公司 | Preparation method of supported rhenium catalyst for preparing alpha-olefin by high-carbon olefin disproportionation |
| CN103801347A (en) * | 2012-11-12 | 2014-05-21 | 中国科学院大连化学物理研究所 | Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst |
| CN104549232A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Rhenium-based disproportionation catalyst |
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