CN104557399A - Method for preparing propylene from pentene and ethylene by disproportionation - Google Patents
Method for preparing propylene from pentene and ethylene by disproportionation Download PDFInfo
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- CN104557399A CN104557399A CN201310512568.7A CN201310512568A CN104557399A CN 104557399 A CN104557399 A CN 104557399A CN 201310512568 A CN201310512568 A CN 201310512568A CN 104557399 A CN104557399 A CN 104557399A
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- amylene
- ethene
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a method for preparing propylene from pentene and ethylene by disproportionation, and mainly solves the problem of low pentene conversion rate in the prior art. The raw materials amylene and ethylene in a mole ratio of 1:(1-6) contact a catalyst to react in a fixed-bed reactor at 20-100 DEG C under the reaction pressure of 0.1-1 MPa to generate a propylene-containing effluent, wherein the weight hourly space velocity of the amylene is 0.5-6 H<-1>, and the catalyst contains 3-20 parts by weight of rhenium oxide and 80-97 parts by weight of alumina support. The technical scheme well solves the problem, and can be used for industrial production of propylene from amylene and ethylene by disproportionation.
Description
Technical field
The present invention relates to a kind of method of amylene and ethene disproportionation propylene.
Background technology
Olefin dismutation reaction is also known as replacement(metathesis)reaction or metathesis reaction, be original C=C bond rupture between two reaction olefin hydrocarbon molecules, the process generating and there is new C=C double bond olefin hydrocarbon molecules of recombinating, utilize olefin dismutation reaction some comparatively cheap, abundant olefin feedstocks can be converted into the higher olefin product of multiple added value.Olefin dismutation reaction process can be represented with following reaction formula:
R in reaction formula
1, R
2, R
3, R
4represent different alkyl or hydrogen atom respectively.If wherein the disproportionation reaction (such as formula 1) of same alkene is called self disproportionation (self-metathesis); Disproportionation reaction (formula 2) between different alkene is then called cross disproportionation (cross-metathesis).
Utilize the cross disproportionation effect of amylene and ethene, by adding appropriate ethene, by relative surplus, C that added value is lower
5olefin feedstock is converted into high added value propylene product.
Olefin dismutation reaction is at VI
b, VII
b, to carry out under metallic compound katalysis in VIII, olefin disproportionation catalyst can be homogeneous catalyst and heterogeneous catalyst, and wherein heterogeneous catalyst typically refers to and is carried on SiO with the form of the oxide compound of Re, Mo or W or a metal-organic complex
2, Al
2o
3, Al
2o
3-SiO
2deng high-ratio surface supported catalyst.Because active metal, support, loaded metal species are different from the factors such as carrier function, make catalyzer in disproportionation reaction, show larger performance difference.
US6271430 discloses the technique that a kind of disproportionation by 1-butylene and 2-butylene obtains propylene and amylene.The catalyzer that this technique adopts is Re
2o
7/ Al
2o
3.Adopt liquid and solid phase reaction, react along with the time increases, transformation efficiency and selectivity all decline.US6166279 adopts identical Re
2o
7/ Al
2o
3catalyzer, reactor is moving-bed, and adopt ethene and amylene to react two reactors, this catalyst regeneration exists certain difficulty simultaneously.
US3767565 discloses a kind of method improving fuel octane number, is wherein comprising WO
3/ SiO
2with on the catalyzer of MgO by the C of olefinic fuel
5fraction and ethene react, and form ethene, propylene, n-butylene and iso-butylene, by gained propylene in addition disproportionation, then gained n-butylene and Trimethylmethane are carried out alkylation.
CN1490289A discloses a kind of method of preparing propylene by butene disproportionation, adopts with SiO
2for carrier, load WO
3fixed bed catalyst, and specific surface area of catalyst is 270 ~ 550 meters
2/ gram, temperature of reaction 250 ~ 450 oC, reaction pressure 0 ~ 10 MPa, liquid phase air speed 0.1 ~ 1.0 hour
-1there is disproportionation reaction under condition and generate propylene.
If CN1228404A discloses the preparation of the 1-butylene of propylene and needs, comprising: a) at VI
b, VII
b, or under at least one displacement catalyzer of VIII transition metal exists, make 1-butylene and 2-butylene reaction, generate propylene and 2-amylene; B) then separated product; C) under a) identical with step again catalyzer exists, make this 2-amylene and ethylene reaction, generate propylene and 1-butylene; D) then separated product; E) 1-butylene that small part is formed is discarded to, and/or at least part of isomerization of formed 1-butylene is made under isomerization catalyst exists, obtain 2-butylene, then by the 1-butylene of not releasing and the 2-butylene that formed and a) the unreacted C of part in step
4fraction returns step a) together.
CN102614867A discloses a kind of mesoporous and olefin metathesis catalyzer that is macropore combined porous structure of simultaneously having, comprise catalytically-active metals and the support of the catalyst of at least one in the oxide compound being selected from rhenium, molybdenum, tungsten, described support of the catalyst is the aluminum oxide with mesopore/macropore combined pore passage structure, described mesoporous aperture is 2 ~ 25 nm, and the aperture of described macropore is 50 ~ 5000 nm; Specific surface area is greater than 200 m
2/ g, pore volume is 0.6 ~ 1.8 cm
3/ g, its intermediary hole accounts for 40% ~ 90% of total pore volume, and macropore accounts for 10% ~ 60% of total pore volume, macropore passing hole window or to be mesoporously connected.Described support of the catalyst is by aluminum contained compound and mesoporous template and the mixing of macroporous granules template, roasting and preparing.Above-mentioned catalyzer solves in conventional art exists in low-carbon alkene disproportionation that catalyst activity is low, inactivation problem faster.Also disclose the preparation method of described olefin metathesis catalyzer.
CN101172925A discloses a kind of method of ethene and producing propene from butylene by disproportion.With ethene, butylene for raw material, the weight ratio of ethene and butylene is 0.1 ~ 3:1, and first ethene contact with catalyzer 1 with first strand of butylene, generates first strand of reaction effluent; After first strand of reaction effluent mixes with second strand of butylene, contact the second strand of reaction effluent generated containing propylene with catalyzer 2; Wherein catalyzer 1 or catalyzer 2 include SiO
2carrier and carry thereon count with vehicle weight 0.1 ~ 30% Tungsten oxide 99.999.
CN1611297A discloses a kind of catalyzer for preparing propylene by butene disproportionation, butene feedstock can be 1-butylene, 2-butylene and composition thereof or the c4 fraction from steam cracking device, copper or its oxide component is added in oxidation tungsten/silicon dioxide catalyst system, achieve good technique effect, can be used in the industrial production of preparing propylene by butene disproportionation.
Above-mentioned document is mainly used in the disproportionation reaction of butylene and ethene, all there is the problem that catalyst activity is low.
Summary of the invention
Technical problem to be solved by this invention is the problem that the pentene conversion that exists in prior art is low, provides a kind of method of new amylene and ethene disproportionation propylene.When the method is used for amylene and ethene disproportionation preparation of propene, there is the advantage that pentene conversion is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of amylene and ethene disproportionation propylene, with amylene and ethene for raw material, temperature of reaction 20 ~ 100 oC, reaction pressure 0.1 ~ 1 MPa, amylene weight space velocity 0.5 ~ 6 hour
-1, ethene and amylene mol ratio (1 ~ 6): under 1 condition, raw material generates propylene by beds, and wherein used catalyst is with weight parts, comprises following component:
A) 3 ~ 20 parts of rhenium oxides;
B) 80 ~ 97 parts of alumina supporters.
In technique scheme, temperature of reaction preferred version is 35 ~ 75 oC, and reaction pressure preferred version is 0.2 ~ 0.8 MPa, and amylene weight space velocity preferred version is 1 ~ 3 hour
-1, the mol ratio preferred version of ethene and amylene is (2 ~ 4): 1, and the preferred version of rhenium oxide parts by weight is 5 ~ 15 parts, and more preferably scheme is 9 ~ 12 parts; It is 85 ~ 95 parts with the preferable range of weight parts aluminum oxide consumption; With weight parts, catalyzer preferably also comprises the lanthanide metal oxide of 0.01 ~ 1 part, more preferably the scope of lanthanide metal oxide content is 0.1 ~ 0.5 part, and at least one in the preferred autoxidation lanthanum of lanthanide metal oxide, cerium oxide and lutecium oxide, is more preferably lutecium oxide.
The catalyzer used in the inventive method is prepared according to following methods:
(1) to Al
2o
3in add sesbania powder and aqueous nitric acid, after 2 ~ 8 hours, make support of the catalyst through kneading, shaping, dry, 500 ~ 700 oC roastings; (2) by described support of the catalyst load ammonium perrhenate or perrhenic acid, drying and 500 ~ 600 oC roastings 2 ~ 6 hours, make described amylene and ethene disproportionation catalyst for preparing propene.
In above-mentioned rhenium base disproportionation catalyst, the content of oxide species is measured by X ray fluorescence spectrometer (XRF).After sample compression molding, at ZSX-100e 4580 type XRF(Rigaku) the upper characteristic spectral line intensity measuring atom, thus obtain the content of oxide species in sample.
The present invention, by adopting amylene and ethene to be raw material, by the active centre of selective oxidation rhenium as disproportionation reaction, has higher catalytic activity and productivity of propylene under lower temperature of reaction.Select suitable activity component load quantity and reaction conditions, effectively can improve the activity and selectivity of catalyzer.The lanthanide metal oxide added and active ingredient and carrier interact, and improve the reactivity worth of catalyzer further.Temperature of reaction 20 ~ 100 oC, reaction pressure 0.1 ~ 1 MPa, amylene weight space velocity 0.5 ~ 6 hour
-1, ethene and amylene mol ratio (1 ~ 6): under 1 condition, raw material is by beds, and its pentene conversion reaches 99.5%, and the molar selectivity of propylene and 1-butylene is respectively 54.2% and 42.9%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.1 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.9967 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 60 oC, reaction pressure 0.6 MPa, amylene weight space velocity 2 hours
-1, ethene and amylene mol ratio 2:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as SSL-1.
[embodiment 2]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
8.8 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 1.3290 grams of ammonium perrhenates, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 50 oC, reaction pressure 0.2 MPa, amylene weight space velocity 3 hours
-1, ethene and amylene mol ratio 4:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as SSL-2.
[embodiment 3]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.5 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.5537 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 35 oC, reaction pressure 0.8 MPa, amylene weight space velocity 4 hours
-1, ethene and amylene mol ratio 2:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as SSL-3.
[embodiment 4]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
8.5 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 1.6612 grams of ammonium perrhenates, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 75 oC, reaction pressure 0.5 MPa, amylene weight space velocity 0.5 hour
-1, ethene and amylene mol ratio 1:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as SSL-4.
[embodiment 5]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.7 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.3322 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 20 oC, reaction pressure 0.1MPa, amylene weight space velocity 1 hour
-1, ethene and amylene mol ratio 1:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as SSL-5.
[embodiment 6]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
7.99 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 2.2150 grams of ammonium perrhenates, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0035 gram of saltpetre, in left at room temperature 24 hours, dry, 520 oC roastings were after 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 100 oC, reaction pressure 1MPa, amylene weight space velocity 6 hours
-1, ethene and amylene mol ratio 6:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as SSL-6.
[embodiment 7]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.07 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.9967 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0797 gram of lanthanum nitrate hexahydrate, in left at room temperature 24 hours, dry, 520 oC roastings were after 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Evaluating catalyst condition is identical with embodiment 1, and reaction result lists in table 1, is designated as SSL-7.
[embodiment 8]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.07 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.9967 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0956 gram of ceric ammonium nitrate, in left at room temperature 24 hours, dry, 520 oC roastings were after 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Evaluating catalyst condition is identical with embodiment 1, and reaction result lists in table 1, is designated as SSL-8.
[embodiment 9]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.07 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.9967 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0571 gram of lutecium nitrate, in left at room temperature 24 hours, dry, 520 oC roastings were after 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Evaluating catalyst condition is identical with embodiment 1, and reaction result lists in table 1, is designated as SSL-9.
[embodiment 10]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.05 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.9967 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0952 gram of lutecium nitrate, in left at room temperature 24 hours, dry, 520 oC roastings were after 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Evaluating catalyst condition is identical with embodiment 1, and reaction result lists in table 1, is designated as SSL-10.
[embodiment 11]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.09 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.9967 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0190 gram of lutecium nitrate, in left at room temperature 24 hours, dry, 520 oC roastings were after 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Evaluating catalyst condition is identical with embodiment 1, and reaction result lists in table 1, is designated as SSL-11.
[embodiment 12]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.099 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.9967 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 0.0019 gram of lutecium nitrate, in left at room temperature 24 hours, dry, 520 oC roastings were after 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Evaluating catalyst condition is identical with embodiment 1, and reaction result lists in table 1, is designated as SSL-12.
[embodiment 13]
By 20 grams of Al
2o
3mix with 0.5 gram of sesbania powder, adding 15 gram mass concentration is the aqueous nitric acid of 2%, is extruded into the cylindrical of diameter 1 millimeter after abundant kneading, and drying, 600 oC roastings, after 5 hours, make the support of the catalyst of 2 ~ 3 millimeters long.
9.099 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 0.9967 gram of ammonium perrhenate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 7.5 milliliters of aqueous solution containing 1.9048 grams of lutecium nitrates, in left at room temperature 24 hours, dry, 520 oC roastings were after 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Evaluating catalyst condition is identical with embodiment 1, and reaction result lists in table 1, is designated as SSL-13.
[comparative example 1]
By silica gel (10 ~ 20 orders, SiO
2content is 99.9%) in atmosphere in 550 oC roasting 4 hours, obtained support of the catalyst.
9.2 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 9.30 gram of six ammonium metatungstate hydrate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 260 oC, reaction pressure 3 MPa, amylene weight space velocity 1 hour
-1, ethene and amylene mol ratio 1:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as BJL-1.
[comparative example 2]
By silica gel (10 ~ 20 orders, SiO
2content is 99.9%) in atmosphere in 550 oC roasting 4 hours, obtained support of the catalyst.
8.8 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 13.96 gram of six ammonium metatungstate hydrate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 300 oC, reaction pressure 2 MPa, amylene weight space velocity 2 hours
-1, ethene and amylene mol ratio 2:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as BJL-2.
[comparative example 3]
By silica gel (10 ~ 20 orders, SiO
2content is 99.9%) in atmosphere in 550 oC roasting 4 hours, obtained support of the catalyst.
8 grams of said catalyst carrier be impregnated in 50 milliliters containing in the aqueous solution of 23.26 gram of six ammonium metatungstate hydrate, put into rotatory evaporator, rotate after 6 hours to moisture evaporate to dryness in 70 oC water-baths.Drying and 520 oC roastings 4 hours, obtained catalyzer.
In catalyzer, the content of oxide species is measured by XRF and obtains, in table 1.
Temperature of reaction 400 oC, reaction pressure 1 MPa, amylene weight space velocity 4 hours
-1, ethene and amylene mol ratio 3:1 condition under carry out catalyst test, reaction result lists in table 1, is designated as BJL-3.
Table 1
Claims (10)
1. a method for amylene and ethene disproportionation propylene, with amylene and ethene for raw material, temperature of reaction 20 ~ 100 oC, reaction pressure 0.1 ~ 1 MPa, amylene weight space velocity 0.5 ~ 6 hour
-1, ethene and amylene mol ratio (1 ~ 6): under 1 condition, raw material generates propylene by beds, and wherein used catalyst is with weight parts, comprises following component:
A) 3 ~ 20 parts of rhenium oxides;
B) 80 ~ 97 parts of alumina supporters.
2. the method for amylene according to claim 1 and ethene disproportionation propylene, is characterized in that temperature of reaction is 35 ~ 75 oC, reaction pressure is 0.2 ~ 0.8 MPa, amylene weight space velocity is 1 ~ 3 hour
-1, ethene and amylene mol ratio (2 ~ 4): 1.
3. the method for amylene according to claim 1 and ethene disproportionation propylene, is characterized in that with weight parts rhenium oxide consumption be 5 ~ 15 parts.
4. the method for amylene according to claim 3 and ethene disproportionation propylene, is characterized in that with weight parts rhenium oxide consumption be 9 ~ 12 parts.
5. the method for amylene according to claim 1 and ethene disproportionation propylene, is characterized in that with weight parts aluminum oxide consumption be 85 ~ 95 parts.
6. the method for the amylene according to any one of claim 1 ~ 5 and ethene disproportionation propylene, is characterized in that with weight parts, also comprises the lanthanide metal oxide of 0.01 ~ 1 part in catalyzer.
7. the method for amylene according to claim 6 and ethene disproportionation propylene, is characterized in that with weight parts, and in catalyzer, the content of lanthanide metal oxide is 0.1 ~ 0.5 part.
8. the method for amylene according to claim 6 and ethene disproportionation propylene, is characterized in that in catalyzer, lanthanide metal oxide is selected from least one in lanthanum trioxide, cerium oxide and lutecium oxide.
9. the method for amylene according to claim 8 and ethene disproportionation propylene, is characterized in that in catalyzer, lanthanide metal oxide is lutecium oxide.
10. the method for amylene according to claim 1 and ethene disproportionation propylene, the preparation method of catalyzer comprises the following steps successively:
(1) to Al
2o
3in add sesbania powder and aqueous nitric acid, after 2 ~ 8 hours, make support of the catalyst through kneading, shaping, dry, 500 ~ 700 oC roastings;
(2) by described support of the catalyst load ammonium perrhenate or perrhenic acid, drying and 500 ~ 600 oC roastings 2 ~ 6 hours, make described amylene and ethene disproportionation catalyst for preparing propene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112679309B (en) * | 2019-10-18 | 2022-11-04 | 中国石油化工股份有限公司 | Method for producing propylene by olefin disproportionation |
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