CN106607067A - Olefin disproportionation catalyst - Google Patents
Olefin disproportionation catalyst Download PDFInfo
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- CN106607067A CN106607067A CN201510686241.0A CN201510686241A CN106607067A CN 106607067 A CN106607067 A CN 106607067A CN 201510686241 A CN201510686241 A CN 201510686241A CN 106607067 A CN106607067 A CN 106607067A
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Abstract
The invention relates to an olefin disproportionation catalyst. The catalyst mainly solves the problem that the existing catalyst has low disproportionation activity. The olefin disproportionation catalyst comprises, by weight, a) 0.01 to 10 parts of a phosphorus element or an oxide thereof, b) 1 to 20 parts of a rhenium element or an oxide thereof, and c) 60 to 99 parts of alumina. The catalyst well solves the problem and can be used for industrial production of an olefin disproportionation reaction.
Description
Technical field
The present invention relates to a kind of olefin disproportionation catalyst.
Technical background
Olefin dismutation reaction also known as metathesis reaction or metathesis reaction, be two reaction olefin hydrocarbon molecules between original C=C bond fissions,
Restructuring generates the process with new C=C double bond olefin hydrocarbon molecules, can be relatively inexpensive, rich by some using olefin dismutation reaction
Rich olefin feedstock is converted into the higher olefin product of various added values.Olefin dismutation reaction can be represented with following reaction equation
Process：
R in reaction equation1, R2, R3, R4Different alkyl or hydrogen atom are represented respectively.If wherein same alkene
Dismutation reaction (such as formula 1) is referred to as itself disproportionation (self-metathesis)；And the dismutation reaction (formula 2) between different alkene
Then it is referred to as cross disproportionation (cross-metathesis).
Acted on using the cross disproportionation of amylene and ethylene, can by adding appropriate ethylene, by relative surplus, added value it is relatively 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 typically referred to the oxide of Re, Mo or W for homogeneous catalyst and heterogeneous catalyst, wherein heterogeneous catalyst
Or the form of metal organic complex is carried on SiO2、Al2O3、Al2O3-SiO2Deng high-ratio surface supported catalyst.By
In the different of the factor such as active metal, support, carried metal species and carrier function so that catalyst is in dismutation reaction
In show larger performance difference.
US6271430 discloses the technique that a kind of disproportionation by 1-butylene and 2-butylene obtains propylene and amylene.The technique
The catalyst for adopting is for Re2O7/Al2O3.Using liquid and solid phase reaction, reaction increases over time, conversion ratio and selectivity all under
Drop.US6166279 adopts identical Re2O7/Al2O3Catalyst, reactor is moving bed, while anti-with amylene using ethylene
Two reactors are answered, the catalyst regeneration has certain difficulty.
US3767565 discloses a kind of method of raising 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 third
Alkene is disproportionated, then gained n- butylene and iso-butane are alkylated.
CN1490289A discloses a kind of method of preparing propylene by butene disproportionation, adopts with SiO2For carrier, WO is loaded3's
Fixed bde catalyst, and specific surface area of catalyst is 270～550 meters2/ gram, in 250～450 DEG C of reaction temperature, reaction pressure
0～10MPa of power, liquid phase air speed 0.1～1.0 hour-1Under the conditions of occur dismutation reaction generate propylene.
CN1228404A discloses the preparation of propylene and 1-butylene if desired, including：A) in VIb、VIIbOr
In the presence of at least one displacement catalyst of VIII transition metal, 1-butylene and 2-butylene reaction are made, generate propylene and 2-
Amylene；B) then separation product；C) again with step a) identical catalyst in the presence of, make the 2- amylenes and ethylene reaction, it is raw
Into propylene and 1-butylene；D) it is then peeled off product；E) 1-butylene at least partly being formed is released, and/or in isomerization catalytic
At least part of isomerization of formed 1-butylene is made in the presence of agent, 2-butylene is obtained, then by the 1-butylene being not bled off and institute's shape
Into 2-butylene and a) the unreacted C in part in step4Fraction return to step a) together.
CN102614867A discloses a kind of while with mesoporous and macropore combined porous structure olefin(e) disproportionation catalyst, bag
The catalytically-active metals and catalyst carrier selected from least one of rhenium, molybdenum, the oxide of tungsten are included, the catalyst carrier is
Aluminium oxide with mesopore/macropore combined pore passage structure, the mesoporous aperture is 2～25nm, and the aperture of the macropore is
50～5000nm；Specific surface area is more than 200m2/ g, pore volume is 0.6～1.8cm3/ g, its intermediary hole account for total pore volume 40%～
90%, macropore accounts for the 10%～60% of total pore volume, and macropore is by hole window or mesoporous is connected.The catalyst carrier is by containing
Aluminium compound and mesoporous template and the mixing of macroporous granules template, roasting and prepare.Above-mentioned catalyst solve with
There are problems that catalyst activity is low in low-carbon alkene disproportionation toward technology, inactivate faster.Also disclose the olefin(e) disproportionation to use
The preparation method of catalyst.
A kind of method that CN101172925A discloses ethylene and producing propene from butylene by disproportion.With ethylene, butylene as raw material,
Ethylene is 0.1～3 with the weight ratio of butylene：1, ethylene is contacted first with first strand of butylene with catalyst 1, generates first strand
Reaction effluent；After first strand of reaction effluent mixes with second strand of butylene, contact with catalyst 2 and generate containing propylene the
Two strands of reaction effluents；Wherein catalyst 1 or catalyst 2 include SiO2Carrier and it is loaded in being calculated as with vehicle weight thereon
0.1～30% tungsten oxide.
CN1611297A discloses a kind of catalyst for preparing propylene by butene disproportionation, and butene feedstock can be 1-butylene, 2- fourths
Alkene and its mixture or the c4 fraction from steam cracking device, oxidation tungsten/silicon dioxide catalyst system and catalyzing in add copper or its
Oxide component, achieves preferable technique effect, in can be used for the commercial production of preparing propylene by butene disproportionation.
Above-mentioned document is mainly used in the dismutation reaction of butylene and ethylene, there is catalyst activity and Propylene Selectivity is low asks
Topic.
The content of the invention
The technical problem to be solved is the low problem of the activity of catalyst disproportionation present in prior art, there is provided a kind of
New olefin disproportionation catalyst.When the catalyst is used for amylene with ethylene disproportionation preparation of propene, with catalyst disproportionation activity
High advantage.
To solve above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of olefin disproportionation catalyst, with weight portion
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 oxidies.
In above-mentioned technical proposal, in terms of parts by weight, the preferred scope of P elements or its oxide is 0.1～8 part, P elements
Or the most preferred range of its oxide is 1～5 part；The preferred scope of rhenium element or its oxide is 5～15 parts；Aluminium oxide
Preferred scope be 70～85 parts；Above-mentioned olefin disproportionation catalyst, the magnesium unit in terms of parts by weight, also including 0.01～1 part
Element or its oxide, its preferred scope is 0.05～0.1 part；Described olefin disproportionation catalyst is used for into amylene and ethylene discrimination
Change propylene processed to react, with amylene and ethylene as raw material, 20～100 DEG C of reaction temperature, 0.1～1MPa of reaction pressure, penta
Alkene weight space velocity 0.5～6 hour-1, ethylene and amylene mol ratio (1～6)：Reaction under the conditions of 1 generates propylene；Wherein,
Reaction temperature preferred scope be 35～70 DEG C, reaction pressure preferred scope be 0.3～0.6MPa, the preferred model of amylene weight space velocity
Enclose for 1～3 hour-1, the mol ratio preferred scope of ethylene and amylene is (2～4)：1.
The preparation method of olefin disproportionation catalyst, comprises the following steps successively in the present invention：
(1) to Al2O3Middle addition sesbania powder and aqueous solution of nitric acid, Jing kneadings, molding, drying, 500～700 DEG C of roastings 2～
After 8 hours, catalyst carrier is made；(2) catalyst carrier is loaded into phosphoric acid, ammonium dihydrogen phosphate or diammonium phosphate,
Drying and 500～600 DEG C of roastings 2～6 hours, make catalyst intermediate；(3) catalyst intermediate is loaded
Ammonium perrhenate or perrhenic acid, drying and 500～600 DEG C of roastings 2～6 hours, make the olefin disproportionation catalyst.
The content of oxide species is determined by Xray fluorescence spectrometer (XRF) in above-mentioned olefin disproportionation catalyst.By sample pressure
After sheetmolding, the characteristic spectral line intensity of atom is determined on types XRF of ZSX-100e 4580 (Rigaku), so as to obtain
The content of oxide species in sample.
The present invention, as the promoter of olefin disproportionation catalyst, makes acid amount and the acid strength increase of catalyst, together by using phosphorus
When improve the reduction temperature of catalyst, so as to effectively increase the reactivity of olefin disproportionation catalyst, enhance catalyst
Stability.By catalyst of the present invention be used for amylene and ethylene propylene reaction, 20～100 DEG C of reaction temperature,
0.1～1MPa of reaction pressure, weight space velocity 0.5～6 hour-1, ethylene and amylene mol ratio (1～6)：Under the conditions of 1,
Up to 99.8%, the molar selectivity of propylene and 1-butylene is respectively 50.7% and 49.1% to pentene conversion, achieves preferably
Technique effect.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
By 20 grams of Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
9.099 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.0014 gram of phosphorus aqueous acid, it is quiet at room temperature
Put 24 hours, be dried, after 520 DEG C of roastings 4 hours, make catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-1 is obtained.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
With 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 mol ratio of ethylene and amylene is 3：Evaluating catalyst is carried out under the conditions of 1, reaction result is listed in table 1.
【Embodiment 2】
By 20 grams of Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.1 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 1.38 grams of phosphorus aqueous acids, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-2 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
9.09 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.014 gram of phosphorus aqueous acid, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-3 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.3 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 1.105 grams of phosphorus aqueous acids, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-4 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
9 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.138 gram of phosphorus aqueous acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-5 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.6 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.69 gram of phosphorus aqueous acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-6 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.799 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.414 gram of phosphorus aqueous acid, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 impregnated in 7.5 milliliters of aqueous solutions containing 0.0037 gram of magnesium nitrate, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-7 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.7 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.414 gram of phosphorus aqueous acid, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 impregnated in 7.5 milliliters of aqueous solutions containing 0.368 gram of magnesium nitrate, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-8 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.795 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.414 gram of phosphorus aqueous acid, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 impregnated in 7.5 milliliters of aqueous solutions containing 0.0184 gram of magnesium nitrate, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-9 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.79 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.414 gram of phosphorus aqueous acid, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 impregnated in 7.5 milliliters of aqueous solutions containing 0.037 gram of magnesium nitrate, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-10 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.999 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 1.243 grams of phosphorus aqueous acids, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 impregnated in 7.5 milliliters of aqueous solutions containing 0.104 gram of perrhenic acid, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 impregnated in 7.5 milliliters of aqueous solutions containing 0.0024 gram of copper nitrate, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-11 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
7.2 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 1.105 grams of phosphorus aqueous acids, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 2.074 grams of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-12 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.9 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.828 gram of phosphorus aqueous acid, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 0.519 gram of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-13 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
8.1 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 0.552 gram of phosphorus aqueous acid, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 1.556 grams of perrhenic acid, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, catalyst SSL-14 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
9.1 grams of said catalyst carriers impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, it is quiet at room temperature
Put 24 hours, be dried, after 520 DEG C of roastings 4 hours, catalyst BJL-1 be obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
7.5 grams of said catalyst carriers be impregnated in into 7.5 milliliters containing in 2.209 grams of phosphorus aqueous acids, stood at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in into 7.5 milliliters containing in 0.9335 phosphorus aqueous acid, 24 are stood at room temperature little
When, it is dried, after 520 DEG C of roastings 4 hours, catalyst BJL-2 is obtained.
The content of oxide species is determined by XRF and obtained 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 Al2O3With 0.5 gram of sesbania powder mix homogeneously, the aqueous solution of nitric acid for adding 15 gram mass concentration to be 2%, fill
It is extruded into the cylinder of 1 millimeter of diameter after point kneading, after drying, 600 DEG C of roastings 5 hours, makes 2～3 millimeters long
Catalyst carrier.
9 grams of said catalyst carriers impregnated in 7.5 milliliters of aqueous solutions containing 0.9335 gram of perrhenic acid, stand at room temperature
24 hours, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 7.5 milliliters of aqueous solutions containing 0.0233 gram of zinc nitrate, 24 are stood at room temperature
Hour, it is dried, after 520 DEG C of roastings 4 hours, makes catalyst BJL-3.
The content of oxide species is determined by XRF and obtained 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 appreciation condition, reaction result is listed in table 2.
Table 2
Claims (10)
1. a kind of olefin disproportionation catalyst, in terms of 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) 60～99 parts of aluminium oxidies.
2. olefin disproportionation catalyst according to claim 1, it is characterised in that P elements or its oxygen in terms of parts by weight
The content of compound is 0.1～8 part.
3. olefin disproportionation catalyst according to claim 1, it is characterised in that P elements or its oxygen in terms of parts by weight
The content of compound is 1～5 part.
4. olefin disproportionation catalyst according to claim 3, it is characterised in that rhenium element or its oxygen in terms of parts by weight
The content of compound is 5～15 parts.
5. olefin disproportionation catalyst according to claim 1, it is characterised in that the content of aluminium oxide in terms of parts by weight
For 70～85 parts.
6. the olefin disproportionation catalyst according to any one of Claims 1 to 5, it is characterised in that also wrapped in terms of parts by weight
Include 0.01～1 part magnesium elements or its oxide.
7. olefin disproportionation catalyst according to claim 6, it is characterised in that magnesium elements or its oxygen in terms of parts by weight
The content of compound is 0.05～0.1 part.
8. the olefin disproportionation catalyst described in any one of claim 1～7 is used for into amylene and ethylene disproportionation preparation of propene,
With amylene and ethylene as raw material, 20～100 DEG C of reaction temperature, 0.1～1MPa of reaction pressure, amylene weight space velocity 0.5～
6 hours-1, ethylene and amylene mol ratio (1～6)：Reaction under the conditions of 1 generates propylene.
9. the purposes of the olefin disproportionation catalyst described in claim 8, it is characterised in that amylene and ethylene are disproportionated propylene processed
35～70 DEG C of the reaction temperature of reaction, 0.3～0.6MPa of reaction pressure, amylene weight space velocity 1～3 hour-1, ethylene and penta
The mol ratio of alkene is (2～4)：1.
10. the preparation method of the olefin disproportionation catalyst described in claim 1, comprises the following steps successively：
(1) to Al2O3Middle addition sesbania powder and aqueous solution of nitric acid, Jing kneadings, molding, drying, 500～700 DEG C of roastings 2～
After 8 hours, catalyst carrier is made；
(2) catalyst carrier is loaded into phosphoric acid, ammonium dihydrogen phosphate or diammonium phosphate, drying and 500～600 DEG C of roastings
Burn 2～6 hours, make catalyst intermediate；
(3) catalyst intermediate is loaded into ammonium perrhenate or perrhenic acid, drying and 500～600 DEG C of roastings 2～6 are little
When, make the olefin disproportionation catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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-olefins 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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-olefins 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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