CN104557399B - The method that amylene is disproportionated propylene processed with ethene - Google Patents
The method that amylene is disproportionated propylene processed with ethene Download PDFInfo
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Abstract
The present invention relates to a kind of method that amylene and ethene are disproportionated propylene processed, the problem of pentene conversion present in prior art is low is mainly solved.The present invention is by using using amylene and ethene as raw material, in fixed bed reactors, the oC of reaction temperature 20~100, the MPa of reaction pressure 0.1~1, amylene weight space velocity 0.5~6 hour‑1, ethene and amylene mol ratio（1~6）：Under the conditions of 1, the effluent of raw material and the generation of catalyst haptoreaction containing propylene, wherein used catalyst technical scheme containing 3~20 parts of rheium oxides and 80~97 parts of alumina supports in terms of parts by weight, preferably solves the problem, is disproportionated available for amylene and ethene in the industrial production of propylene processed.
Description
Technical field
The present invention relates to a kind of method that amylene and ethene are disproportionated propylene processed.
Background technology
Olefin dismutation reaction is also known as metathesis reaction or metathesis reaction, be two reaction olefin hydrocarbon molecules between original C=C keys break
Split, recombinate generation with new C=C double bond olefin hydrocarbon molecules process, using olefin dismutation reaction can some are relatively inexpensive,
Abundant olefin feedstock is converted into the higher olefin product of a variety of added values.It can represent that olefin(e) disproportionation is anti-with following reaction equation
Answer process：
R in reaction equation1, R2, R3, R4Different alkyl or hydrogen atom are represented respectively.If wherein same alkene
Disproportionated reaction（Such as formula 1）Referred to as itself is disproportionated (self-metathesis)；And the disproportionated reaction between different alkene（Formula 2）
Then it is referred to as cross disproportionation (cross-metathesis).
Using amylene and ethene cross disproportionation act on, can by adding appropriate ethene, by relative surplus, added value compared with
Low C5Olefin feedstock is converted into high added value propylene product.
Olefin dismutation reaction is in VIB、VIIB, carry out under metallic compound catalytic action in VIII, olefin(e) disproportionation is urged
Agent can be homogeneous catalyst and heterogeneous catalyst, and wherein heterogeneous catalyst typically refers to the oxide or gold with Re, Mo or W
The form of category organic coordination compound is carried on SiO2、Al2O3、Al2O3-SiO2Deng the catalyst on high surface area carrier.Due to activity
The difference of the factors such as metal, support, carried metal species and carrier function so that catalyst is shown 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 the technique is used is Re2O7/Al2O3.Using liquid and solid phase reaction, reaction increases over time, conversion ratio and selectivity
All decline.US6166279 uses identical Re2O7/Al2O3Catalyst, reactor is moving bed, while using ethene and amylene
Two reactors are reacted, catalyst regeneration has certain difficulty.
US3767565 discloses a kind of method for improving fuel octane number, wherein including WO3/SiO2With MgO catalysis
By the C of olefinic fuel in agent5Fraction is reacted with ethene, ethene, propylene, n- butylene and isobutene is formed, by gained propylene
It is disproportionated, then gained n- butylene and iso-butane is alkylated.
CN1490289A discloses a kind of method of preparing propylene by butene disproportionation, uses with SiO2For carrier, WO is loaded3Consolidate
Bed catalyst, and specific surface area of catalyst is 270~550 meters2/ gram, the oC of reaction temperature 250~450, reaction pressure 0~
10 MPa, liquid phase air speed 0.1~1.0 hour-1Under the conditions of occur disproportionated reaction generation 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, make 1- butylene and 2- butene reactions, generation propylene and 2- penta
Alkene；B) then separation product；C) again with the presence of step a) identical catalyst, making the 2- amylenes and ethylene reaction, generation third
Alkene and 1- butylene；And then separation product d)；E) the 1- butylene at least partly formed is released, and/or is deposited in isomerization catalyst
Make formed 1- butylene at least part isomerization under, obtain 2- butylene, then by the 1- butylene being not bled off and formed
2- butylene and a) the unreacted C in part in step4Fraction return to step a) together.
CN102614867A discloses a kind of while having mesoporous and macropore combined porous structure olefin(e) disproportionation catalyst,
Including catalytically-active metals and catalyst carrier selected from least one of rhenium, molybdenum, the oxide of tungsten, the catalyst carrier is
Aluminum oxide with mesopore/macropore combined pore passage structure, the mesoporous aperture is 2~25 nm, and the aperture of the 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 is by hole window or mesoporous is connected.The catalyst carrier passes through containing calorize
Compound and mesoporous template and macroporous granules template mix, are calcined and prepare.Above-mentioned catalyst solves conventional skill
There is the problem of catalyst activity is low, inactivation is very fast in art in low-carbon alkene disproportionation.Also disclose the olefin(e) disproportionation catalysis
The preparation method of agent.
A kind of method that CN101172925A discloses ethene and producing propene from butylene by disproportion.Using ethene, butylene as raw material,
The weight ratio of ethene and butylene is 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, second strand containing propylene of generation is contacted with catalyst 2 anti-
Answer effluent；Wherein catalyst 1 or catalyst 2 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, copper is added in oxidation tungsten/silicon dioxide catalyst system and catalyzing
Or its oxide component, preferable technique effect is achieved, available in the industrial production of preparing propylene by butene disproportionation.
Above-mentioned document is mainly used in the disproportionated reaction of butylene and ethene, there is the problem of catalyst activity is low.
The content of the invention
The technical problems to be solved by the invention are that there is provided one kind for the problem of pentene conversion is low present in prior art
The method that new amylene is disproportionated propylene processed with ethene.When this method is used for amylene with ethene disproportionation preparation of propene, with amylene
The advantage of high conversion rate.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of amylene is disproportionated propylene processed with ethene
Method, it is empty in the oC of reaction temperature 20~100, the MPa of reaction pressure 0.1~1, amylene weight using amylene and ethene as raw material
Speed 0.5~6 hour-1, ethene and amylene mol ratio（1~6）：Under the conditions of 1, raw material generates propylene by beds, its
Middle used catalyst is in terms of parts by weight, including following components：
A) 3~20 parts of rheium oxides；
B) 80~97 parts of alumina supports.
In above-mentioned technical proposal, reaction temperature preferred scheme is 35~75 oC, and reaction pressure preferred scheme is 0.2~0.8
MPa, amylene weight space velocity preferred scheme is 1~3 hour-1, the mol ratio preferred scheme of ethene and amylene is（2~4）：1, oxidation
The preferred scheme of rhenium parts by weight is 5~15 parts, and more preferably scheme is 9~12 parts；Aluminum oxide consumption is excellent in terms of parts by weight
It is 85~95 parts to select scope；In terms of parts by weight, catalyst preferably also includes 0.01~1 part of lanthanide metal oxide, lanthanum
The more preferably scope of series metal oxide content be 0.1~0.5 part, lanthanide metal oxide preferably be selected from lanthana, cerium oxide and
At least one in luteium oxide, more preferably luteium oxide.
The catalyst used in the inventive method is prepared according to following methods：
(1) to Al2O3Middle addition sesbania powder and aqueous solution of nitric acid, through kneading, shaping, drying, 500~700 oC roastings 2
After~8 hours, catalyst carrier is made；(2) catalyst carrier is loaded into ammonium perrhenate or perrhenic acid, through drying and 500
~600 oC are calcined 2~6 hours, and the amylene is made and is disproportionated catalyst for preparing propene with ethene.
The content of oxide species is by X ray fluorescence spectrometers in above-mentioned rhenium base disproportionation catalyst（XRF）Determine.By sample
After compression molding, in the type XRF of ZSX-100e 4580（Rigaku）The upper characteristic spectral line intensity for determining atom, so as to obtain sample
The content of oxide species in product.
The present invention is raw material by using amylene and ethene, by activated centre of the selective oxidation rhenium as disproportionated reaction,
There is higher catalytic activity and productivity of propylene under relatively low reaction temperature.Select suitable activity component load quantity and reaction
Condition, can effectively improve the activity and selectivity of catalyst.The lanthanide metal oxide of addition and active component and carrier are mutual
Effect, further improves the reactivity worth of catalyst.In the oC of reaction temperature 20~100, the MPa of reaction pressure 0.1~1, amylene
Weight space velocity 0.5~6 hour-1, ethene and amylene mol ratio（1~6）：Under the conditions of 1, raw material is by beds, and it penta
Alkene conversion ratio is up to 99.5%, and the molar selectivity of propylene and 1- butylene is respectively 54.2% and 42.9%, achieves preferable technology effect
Really.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
9.1 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.9967 gram of ammonium perrhenate, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 60, the MPa of reaction pressure 0.6, amylene weight space velocity 2 hours-1, ethene and amylene mol ratio
2：Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as SSL-1.
【Embodiment 2】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
8.8 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 1.3290 grams of ammonium perrhenates, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 50, the MPa of reaction pressure 0.2, amylene weight space velocity 3 hours-1, ethene and amylene mol ratio
4：Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as SSL-2.
【Embodiment 3】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
9.5 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.5537 gram of ammonium perrhenate, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 35, the MPa of reaction pressure 0.8, amylene weight space velocity 4 hours-1, ethene and amylene mol ratio
2：Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as SSL-3.
【Embodiment 4】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
8.5 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 1.6612 grams of ammonium perrhenates, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 75, the MPa of reaction pressure 0.5, amylene weight space velocity 0.5 hour-1, ethene and amylene mole
Than 1：Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as SSL-4.
【Embodiment 5】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
9.7 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.3322 gram of ammonium perrhenate, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 20, reaction pressure 0.1MPa, amylene weight space velocity 1 hour-1, ethene and amylene mol ratio
1：Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as SSL-5.
【Embodiment 6】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
7.99 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 2.2150 grams of ammonium perrhenates, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent intermediate.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solution containing 0.0035 gram of potassium nitrate, it is quiet at room temperature
Put 24 hours, after dry, 520 oC are calcined 4 hours, catalyst is made.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 100, reaction pressure 1MPa, amylene weight space velocity 6 hours-1, ethene and amylene mol ratio 6：
Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as SSL-6.
【Embodiment 7】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
9.07 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.9967 gram of ammonium perrhenate, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent intermediate.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solution containing 0.0797 gram of lanthanum nitrate hexahydrate, in room
Temperature is lower to stand 24 hours, and after dry, 520 oC are calcined 4 hours, catalyst is made.
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, is designated as SSL-7.
【Embodiment 8】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
9.07 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.9967 gram of ammonium perrhenate, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent intermediate.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solution containing 0.0956 gram of ammonium ceric nitrate, at room temperature
24 hours are stood, after dry, 520 oC are calcined 4 hours, catalyst is made.
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, is designated as SSL-8.
【Embodiment 9】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
9.07 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.9967 gram of ammonium perrhenate, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent intermediate.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solution containing 0.0571 gram of lutecium nitrate, it is quiet at room temperature
Put 24 hours, after dry, 520 oC are calcined 4 hours, catalyst is made.
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, is designated as SSL-9.
【Embodiment 10】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, fully
The cylinder of 1 millimeter of diameter is extruded into after kneading, after being calcined 5 hours through drying, 600 oC, catalyst 2~3 millimeters long is made and carries
Body.
9.05 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.9967 gram of ammonium perrhenate, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent intermediate.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solution containing 0.0952 gram of lutecium nitrate, it is quiet at room temperature
Put 24 hours, after dry, 520 oC are calcined 4 hours, catalyst is made.
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, is designated as SSL-10.
【Embodiment 11】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, it is fully mixed
The cylinder of 1 millimeter of diameter is extruded into after pinching, after being calcined 5 hours through drying, 600 oC, 2~3 millimeters of long catalyst carriers are made.
9.09 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.9967 gram of ammonium perrhenate, rotation is put into
Turn in evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, is made and urges
Agent intermediate.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solution containing 0.0190 gram of lutecium nitrate, it is quiet at room temperature
Put 24 hours, after dry, 520 oC are calcined 4 hours, catalyst is made.
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, is designated as SSL-11.
【Embodiment 12】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, it is fully mixed
The cylinder of 1 millimeter of diameter is extruded into after pinching, after being calcined 5 hours through drying, 600 oC, 2~3 millimeters of long catalyst carriers are made.
9.099 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.9967 gram of ammonium perrhenate, are put into
In rotary evaporator, it is evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours, is made with 520 oC through drying
Catalyst intermediate.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solution containing 0.0019 gram of lutecium nitrate, it is quiet at room temperature
Put 24 hours, after dry, 520 oC are calcined 4 hours, catalyst is made.
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, is designated as SSL-12.
【Embodiment 13】
By 20 grams of Al2O3It is well mixed with 0.5 gram of sesbania powder, the aqueous solution of nitric acid that 15 gram mass concentration are 2% is added, it is fully mixed
The cylinder of 1 millimeter of diameter is extruded into after pinching, after being calcined 5 hours through drying, 600 oC, 2~3 millimeters of long catalyst carriers are made.
9.099 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 0.9967 gram of ammonium perrhenate, are put into
In rotary evaporator, it is evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours, is made with 520 oC through drying
Catalyst intermediate.
Above-mentioned catalyst intermediate is impregnated in 7.5 milliliters of aqueous solution containing 1.9048 grams of lutecium nitrates, it is quiet at room temperature
Put 24 hours, after dry, 520 oC are calcined 4 hours, catalyst is made.
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, is designated as SSL-13.
【Comparative example 1】
By silica gel（10~20 mesh, SiO2Content is 99.9%）It is calcined 4 hours in 550 oC in atmosphere, catalyst is made
Carrier.
9.2 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 9.30 gram of six ammonium metatungstate hydrate, put
Enter in rotary evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, system
Obtain catalyst.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 260, the MPa of reaction pressure 3, amylene weight space velocity 1 hour-1, ethene and amylene mol ratio
1：Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as BJL-1.
【Comparative example 2】
By silica gel（10~20 mesh, SiO2Content is 99.9%）It is calcined 4 hours in 550 oC in atmosphere, catalyst is made
Carrier.
8.8 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 13.96 gram of six ammonium metatungstate hydrate, put
Enter in rotary evaporator, be evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours with 520 oC through drying, system
Obtain catalyst.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 300, the MPa of reaction pressure 2, amylene weight space velocity 2 hours-1, ethene and amylene mol ratio
2：Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as BJL-2.
【Comparative example 3】
By silica gel（10~20 mesh, SiO2Content is 99.9%）It is calcined 4 hours in 550 oC in atmosphere, catalyst is made
Carrier.
8 grams of said catalyst carriers are impregnated in 50 milliliters of aqueous solution containing 23.26 gram of six ammonium metatungstate hydrate, are put into
In rotary evaporator, it is evaporated after being rotated 6 hours in 70 oC water-baths to moisture.It is calcined 4 hours, is made with 520 oC through drying
Catalyst.
The content of oxide species is determined by XRF and obtained in catalyst, is shown in Table 1.
In the oC of reaction temperature 400, the MPa of reaction pressure 1, amylene weight space velocity 4 hours-1, ethene and amylene mol ratio
3：Catalyst test is carried out under the conditions of 1, reaction result is listed in table 1, is designated as BJL-3.
Table 1
Claims (8)
1. a kind of method that amylene and ethene are disproportionated propylene processed, using amylene and ethene as raw material, 20~100 DEG C of reaction temperature,
0.1~1MPa of reaction pressure, amylene weight space velocity 0.5~6 hour-1, ethene and amylene mol ratio (1~6)：It is former under the conditions of 1
Material generates propylene by beds, and wherein used catalyst is in terms of parts by weight, including following components：
A) 3~20 parts of rheium oxides；
B) 80~97 parts of alumina supports；
In terms of parts by weight, 0.01~1 part of lanthanide metal oxide is also included in catalyst.
2. the method that amylene according to claim 1 and ethene are disproportionated propylene processed, it is characterised in that reaction temperature for 35~
75 DEG C, reaction pressure be that 0.2~0.8MPa, amylene weight space velocity are 1~3 hour-1, ethene and amylene mol ratio (2~4)：
1。
3. the method that amylene according to claim 1 is disproportionated propylene processed with ethene, it is characterised in that the oxygen in terms of parts by weight
It is 5~15 parts to change rhenium consumption.
4. the method that amylene according to claim 3 is disproportionated propylene processed with ethene, it is characterised in that the oxygen in terms of parts by weight
It is 9~12 parts to change rhenium consumption.
5. the method that amylene according to claim 1 is disproportionated propylene processed with ethene, it is characterised in that the oxygen in terms of parts by weight
It is 85~95 parts to change aluminium consumption.
6. the method that amylene according to claim 1 is disproportionated propylene processed with ethene, it is characterised in that in terms of parts by weight, urge
The content of lanthanide metal oxide is 0.1~0.5 part in agent.
7. the method that amylene according to claim 1 is disproportionated propylene processed with ethene, it is characterised in that group of the lanthanides gold in catalyst
Belong at least one of the oxide in lanthana, cerium oxide and luteium oxide.
8. the method that amylene according to claim 7 is disproportionated propylene processed with ethene, it is characterised in that group of the lanthanides gold in catalyst
Category oxide is luteium oxide.
Priority Applications (1)
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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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