CN104549232B - Rhenium-based disproportionation catalyst - Google Patents
Rhenium-based disproportionation catalyst Download PDFInfo
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- CN104549232B CN104549232B CN201310512685.3A CN201310512685A CN104549232B CN 104549232 B CN104549232 B CN 104549232B CN 201310512685 A CN201310512685 A CN 201310512685A CN 104549232 B CN104549232 B CN 104549232B
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Abstract
The invention relates to a rhenium-based disproportionation catalyst, which is mainly used for solving the problem of low disproportionation activity of a catalyst in the prior art. The problem is better solved through the adoption of the technical scheme that the rhenium-based disproportionation catalyst comprises the following components in parts by weight: a) 1-30 parts of rhenium or a rhenium oxide; b) 0.01-5 parts of zinc or a zinc oxide; and c) 65-99 parts of aluminum oxide. The rhenium-based disproportionation catalyst can be applied to the industrial production of olefin disproportionation reaction.
Description
Technical field
The present invention relates to a kind of rhenium base disproportionation catalyst.
Background technology
Olefin dismutation reaction, also known as metathesis reaction or metathesis reaction, is that between two reaction olefin hydrocarbon molecules, original C=C key breaks
Split, recombinating to generate has the process of new C=C double bond olefin hydrocarbon molecules, using olefin dismutation reaction can some are relatively inexpensive,
Abundant olefin feedstock is converted into the higher olefin product of multiple added values.Olefin(e) disproportionation can be represented with following reaction equation anti-
Answer process：
R in reaction equation1, R2, R3, R4Represent different alkyl or hydrogen atom respectively.If wherein same alkene
Disproportionated reaction（As formula 1）It is referred to as itself disproportionation (self-metathesis)；And the disproportionated reaction between different alkene（Formula 2）
Then it is referred to as cross disproportionation (cross-metathesis).
Using the cross disproportionation effect of amylene and ethene, can be by adding appropriate ethene, by relative surplus, added value relatively
Low C5Olefin feedstock is converted into high added value propylene product.
Olefin dismutation reaction is in VIB、VIIB, carry out under the metallic compound catalytic action in VIII, olefin(e) disproportionation is urged
Agent can be homogeneous catalyst and heterogeneous catalyst, and wherein heterogeneous catalyst typically refers to the oxide of Re, Mo or W or gold
The form belonging to organic coordination compound is carried on SiO2、Al2O3、Al2O3-SiO2Deng high-ratio surface supported catalyst.Due to activity
Metal, support, carried metal species are from the different of the factors such as carrier function so that catalyst shows in disproportionated reaction
Larger performance difference.
US6271430 discloses the technique that a kind of disproportionation by 1- butylene and 2- butylene obtains propylene and amylene.
The catalyst that this technique adopts is Re2O7/Al2O3.Using liquid and solid phase reaction, reaction increases over time, conversion ratio and selectivity
All decline.US6166279 adopts identical Re2O7/Al2O3Catalyst, reactor is moving bed, adopts ethene and amylene simultaneously
Two reactors of reaction, there is certain difficulty in the regeneration of this catalyst.
US3767565 discloses a kind of method improving fuel octane number, is wherein including WO3/SiO2Catalysis with MgO
By the C of olefinic fuel in agent5Fraction is reacted with ethene, forms ethene, propylene, n- butylene and isobutene, 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, adopts with SiO2For carrier, load WO3Consolidate
Bed catalyst, and specific surface area of catalyst is 270～550 meters2/ gram, reaction temperature 250～450 C, reaction pressure 0～
10 MPa, liquid phase air speed 0.1～1.0 hour-1Under the conditions of occur disproportionated reaction generate propylene.
CN1228404A discloses propylene and the preparation of 1- butylene if necessary, including：A) in VIb、VIIb, or
In the presence of at least one displacement catalyst of VIII transition metal, make 1- butylene and 2- butene reaction, generate propylene and 2- penta
Alkene；B) then separation product；C) again with step a) identical catalyst in the presence of, make this 2- amylene and ethylene reaction, generate third
Alkene and 1- butylene；D) it is then peeled off product；E) release the 1- butylene at least partly being formed, and/or deposit in isomerization catalyst
Under make the formed at least part of isomerization of 1- butylene, obtain 2- butylene, then by the 1- being not bled off butylene with formed
Partly unreacted C in 2- butylene and a) step4Fraction return to step a) together.
CN102614867A disclose a kind of there is mesoporous and macropore combined porous structure olefin(e) disproportionation catalyst simultaneously,
Including selected from the catalytically-active metals of at least one of rhenium, molybdenum, the oxide of tungsten and catalyst carrier, described catalyst carrier is
There is the aluminum oxide of mesopore/macropore combined pore passage structure, described mesoporous aperture is 2～25 nm, the aperture of described macropore is 50
～5000 nm；Specific surface area is more than 200 m2/ g, pore volume is 0.6～1.8 cm3/ g, its intermediary hole account for total pore volume 40%～
90%, macropore accounts for the 10%～60% of total pore volume, and macropore passes through hole window or mesoporous is connected.Described catalyst carrier is by containing calorize
Compound and mesoporous template and the mixing of macroporous granules template, roasting and prepare.Above-mentioned catalyst solves conventional skill
Have in low-carbon alkene disproportionation in art that catalyst activity is low, inactivation problem faster.Also disclose described olefin(e) disproportionation catalysis
The preparation method of agent.
A kind of method that CN101172925A discloses ethene and producing propene from butylene by disproportion.With ethene, butylene as raw material,
The weight of ethene and butylene is than for 0.1～3：1, ethene 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, contact second strand generating containing propylene with catalyst 2 anti-
Answer effluent；Wherein catalyst 1 or catalyst 2 all include SiO2Carrier and be loaded in thereon be calculated as 0.1～30% with vehicle weight
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 the c4 fraction from steam cracking device, add copper in oxidation tungsten/silicon dioxide catalyst system and catalyzing
Or its oxide component, achieve preferable technique effect, 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 ethene, all there is catalyst activity and Propylene Selectivity is low
Problem.
Content of the invention
The technical problem to be solved is the low problem of the activity of catalyst disproportionation present in prior art, provides
A kind of new rhenium base disproportionation catalyst.When this catalyst is used for amylene with ethene disproportionation preparation of propene, there is catalyst disproportionation
The high advantage of activity.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of rhenium base disproportionation catalyst, with weight
Number meter, including following components：A) 1～30 part of rhenium element or its oxide；B) 0.01～5 part of Zn-ef ficiency or its oxide；
C) 65～99 parts of aluminum oxide.
In technique scheme, in terms of parts by weight, the preferred scope of rhenium element or its oxide is 4～20 parts；Zinc unit
The preferred scope of element or its oxide is 0.05～3 part, and the most preferred range of Zn-ef ficiency or its oxide is 0.1～0.25 part；
The preferred scope of aluminum oxide is 70～85 parts；Above-mentioned rhenium base disproportionation catalyst, in terms of parts by weight, also includes 0.01～1 part
Calcium constituent or its oxide, its preferred scope is 0.05～0.1 part；Described rhenium base disproportionation catalyst is used for amylene and ethene
Disproportionation preparation of propene, with amylene and ethene as raw material, reaction temperature 20～100 C, reaction pressure 0.1～0.9 MPa,
Amylene weight space velocity 0.5～6 hour-1, the mol ratio of ethene and amylene（1～6）：Under the conditions of 1, reaction generates propylene；Wherein, instead
Temperature preferred scope is answered to be 35～70 C, reaction pressure preferred scope is 0.3～0.6 MPa, amylene weight space velocity preferred scope
For 1～3 hour-1, the mol ratio preferred scope of ethene and amylene is（2～4）：1.
In the present invention, the preparation method of rhenium base disproportionation catalyst, comprises the following steps successively：
(1) to Al2O3Middle addition sesbania powder and aqueous solution of nitric acid, through kneading, shaping, drying, 500～700 C roastings 2
After～8 hours, make catalyst carrier；(2) described catalyst carrier is loaded ammonium perrhenate or perrhenic acid, drying and 500
～600 C roastings 2～6 hours, make catalyst intermediate；(3) solubility containing zinc by the load of described catalyst intermediate
Salt, drying and 500～600 C roastings 2～6 hours, make described rhenium base disproportionation catalyst.
In above-mentioned rhenium base disproportionation catalyst, the content of oxide species is by X ray fluorescence spectrometer（XRF）Measure.By sample
After compression molding, in ZSX-100e 4580 type XRF（Rigaku）The upper characteristic spectral line intensity measuring atom, thus obtain sample
The content of oxide species in product.
The present invention by using zinc as rhenium base disproportionation catalyst auxiliary agent, by the phase interaction between main active component rhenium
With the reactivity of rhenium base disproportionation catalyst can be effectively improved.Catalyst of the present invention is used for amylene and ethene system third
Alkene reaction, in reaction temperature 20～100 C, reaction pressure 0.1～0.9 MPa, weight space velocity 0.5～6 hour-1, ethene and penta
The mol ratio of alkene（1～6）：Under the conditions of 1, pentene conversion reaches 99.5%, and the molar selectivity of propylene and 1- butylene is respectively
50.7% and 49.1%, achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
By 20 grams of Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.199 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0023 gram of zinc nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-1.
In catalyst, the content of oxide species is measured by XRF and obtains, and is shown in Table 1.
With amylene and ethene as raw material, little in reaction temperature 60 C, reaction pressure 0.6 MPa, amylene weight space velocity 2
When-1, the mol ratio of ethene and amylene be 2：Carry out evaluating catalyst, reaction result is listed in table 1 under the conditions of 1.
【Embodiment 2】
By 20 grams of Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
8.7 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 1.1635 grams of zinc nitrates, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-2.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.195 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0116 gram of zinc nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-3.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
8.9 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.6981 gram of zinc nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-4.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.19 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0233 gram of zinc nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-5.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.175 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0582 gram of zinc nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-6.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.174 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 be impregnated in 7.5 milliliters of aqueous solution containing 0.0582 gram of zinc nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 be impregnated in 7.5 milliliters of aqueous solution containing 0.0293 gram of calcium nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, prepared catalyst SSL-7.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.075 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 be impregnated in 7.5 milliliters of aqueous solution containing 0.0582 gram of zinc nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 be impregnated in 7.5 milliliters of aqueous solution containing 2.9261 grams of calcium nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, prepared catalyst SSL-8.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.17 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 be impregnated in 7.5 milliliters of aqueous solution containing 0.0582 gram of zinc nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 be impregnated in 7.5 milliliters of aqueous solution containing 0.1463 gram of calcium nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, prepared catalyst SSL-9.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.165 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 be impregnated in 7.5 milliliters of aqueous solution containing 0.0582 gram of zinc nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 be impregnated in 7.5 milliliters of aqueous solution containing 0.2926 gram of calcium nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, prepared catalyst SSL-10.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.499 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.1037 gram of perrhenic acid, in room temperature
Lower standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -1.
Above-mentioned catalyst intermediate -1 be impregnated in 7.5 milliliters of aqueous solution containing 0.9308 gram of zinc nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate -2.
Above-mentioned catalyst intermediate -2 be impregnated in 7.5 milliliters of aqueous solution containing 0.0024 gram of copper nitrate, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, prepared catalyst SSL-11.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
6.7 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 3.1116 grams of perrhenic acid, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.6981 gram of zinc nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-12.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.4 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.4149 gram of perrhenic acid, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.4654 gram of zinc nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-13.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
7.9 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 2.0744 grams of perrhenic acid, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.2327 gram of zinc nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst SSL-14.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.2 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, prepared catalyst BJL-1.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
8.4 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 1.3962 grams of zinc nitrates, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, prepared catalyst BJL-2.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 Al2O3Mix with 0.5 gram of sesbania powder, add the aqueous solution of nitric acid that 15 gram mass concentration are 2%, fully
It is extruded into the cylinder of 1 millimeter of diameter, after drying, 600 C roasting 5 hours, the catalyst making 2～3 millimeters long carries after kneading
Body.
9.1 grams of said catalyst carrier be impregnated in 7.5 milliliters of aqueous solution containing 0.8298 gram of perrhenic acid, at room temperature
Standing 24 hours, is dried, after 520 C roasting 4 hours, makes catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.3680 gram of magnesium nitrate, quiet at room temperature
Put 24 hours, be dried, after 520 C roasting 4 hours, make catalyst BJL-3.
In catalyst, the content of oxide species is measured by XRF and obtains, and 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 (8)
1. a kind of rhenium base disproportionation catalyst, in terms of parts by weight, including following components：
A) 1～30 part of rhenium element or its oxide；
B) 0.1～0.25 part of Zn-ef ficiency or its oxide；
C) 65～99 parts of aluminum oxide.
2. rhenium base disproportionation catalyst according to claim 1 it is characterised in that in terms of parts by weight rhenium element or its oxidation
The content of thing is 4～20 parts.
3. rhenium base disproportionation catalyst according to claim 1 it is characterised in that in terms of parts by weight the content of aluminum oxide be
70～85 parts.
4. the rhenium base disproportionation catalyst according to any one of claims 1 to 3 is it is characterised in that also included in terms of parts by weight
0.01～1 part of calcium constituent or its oxide.
5. rhenium base disproportionation catalyst according to claim 4 it is characterised in that in terms of parts by weight calcium constituent or its oxidation
The content of thing is 0.05～0.1 part.
6. use in amylene and ethene disproportionation preparation of propene for the rhenium base disproportionation catalyst described in any one of Claims 1 to 5
Way it is characterised in that with amylene and ethene as raw material, in 20～100 DEG C of reaction temperature, reaction pressure 0.1～0.9MPa, amylene
Weight space velocity 0.5～6 hour-1, the mol ratio (1～6) of ethene and amylene：Under the conditions of 1, reaction generates propylene.
7. the purposes of rhenium base disproportionation catalyst according to claim 6 is it is characterised in that amylene and ethene are disproportionated propylene processed
35～70 DEG C of the reaction temperature of reaction, reaction pressure 0.3～0.6MPa, amylene weight space velocity 1～3 hour-1, ethene and amylene
Mol ratio is (2～4)：1.
8. the preparation method of the rhenium base disproportionation catalyst described in claim 1, comprises the following steps successively：
(1) to Al2O3Middle addition sesbania powder and aqueous solution of nitric acid, through kneading, shaping, drying, 500～700 DEG C of roastings 2～8 hours
Afterwards, make catalyst carrier；
(2) described catalyst carrier is loaded ammonium perrhenate or perrhenic acid, drying and 500～600 DEG C of roastings 2～6 hours, system
Become catalyst intermediate；
(3) soluble-salt containing zinc by the load of described catalyst intermediate, drying and 500～600 DEG C of roastings 2～6 hours, system
Become described rhenium base disproportionation catalyst.
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