CN109833915A - Molybdenum loaded catalyst and preparation method thereof for 1- butylene self disproportionation reaction - Google Patents
Molybdenum loaded catalyst and preparation method thereof for 1- butylene self disproportionation reaction Download PDFInfo
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- CN109833915A CN109833915A CN201711210910.2A CN201711210910A CN109833915A CN 109833915 A CN109833915 A CN 109833915A CN 201711210910 A CN201711210910 A CN 201711210910A CN 109833915 A CN109833915 A CN 109833915A
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- molybdenum
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The molybdenum loaded catalyst and preparation method thereof that the present invention provides a kind of for 1- butylene self disproportionation reaction, the catalyst are made of active metal molybdenum component, carrier and polyethylene of dispersing agent pyrrolidones three parts.Dispersion degree of the molybdenum species on carrier is improved by the introducing of dispersing agent, effectively inhibits the generation of double-bond isomerism and other disproportionation side reactions, significantly improves the selectivity of goal response.Catalyst with base of molybdenum prepared by the present invention has the characteristics that goal response selectivity is high and reaction stability is superior, can be used for the industrial production of preparing hexane by disproportionating butylene.
Description
Technical field
The invention belongs to heterogeneous catalysis fields, and in particular to a kind of molybdenum supported catalyst for 1- butylene self disproportionation reaction
Agent and preparation method thereof.
Background technique
1- hexene is the important additives of synthesizing linear low-density polyethylene, has excellent tensile strength, tear-proof strong
Degree, added value are very high.The customary preparation methods of industrial hexene are to be gathered using alkylated metallic catalyst by ethylene at present
It closes reaction and generates 1- hexene.Butylene is the byproduct of naphtha steam cracking, is consumed generally as liquefied petroleum gas.Therefore, lead to
Self disproportionation reaction and the olefin isomerization reaction of butylene are crossed, can be high attached by relative surplus, the lower butenc of added value
Value added hexene and ethylene.
In 1- butylene self disproportionation reaction, due to the effect of catalyst, it is easy to the reaction life of 1- butylene double-bond isomerism occur
At the side reaction of 2- butylene, and 2- butylene can further with the lower amylene of 1- butylene cross disproportionation production added value and centainly
The propylene of amount, which results in the reductions of target product selectivity, and therefore, the key of the technology is that 1- butylene is inhibited to be catalyzed
The double-bond isomerization on agent surface.
US6683019 reports 1- butylene from disproportionation technology.The technology uses W/SiO2As catalyst, wherein carrier
SiO2Purity it is very crucial, easily form the content of acidic site or basic sites element by reducing Al, Fe, Ca etc. on carrier, subtract
The generation of few isomerization reaction, improves the yield of target product hexene and ethylene.
A kind of method that patent CN201210412571.7 reports preparing hexane by disproportionating butylene, invention are original with 1- butylene
Material, reaction temperature is 300~450 DEG C in fixed bed reactors, and reaction pressure is calculated as 0~2.0MPa, weight space velocity with absolute pressure
For 4~20h-1Under the conditions of, raw material and catalyst haptoreaction generate the effluent containing hexene, and wherein used catalyst is with parts by weight
Number meter, including following components: a) 5~50 parts of tungsten oxide；B) 50~95 parts of magnesia.The invention preferably solves catalyst
The low problem of activity, can be used for the industrial production of preparing hexane by disproportionating butylene.
Patent CN201210412530.8 reports a kind of technique comprising hexene processed including feed purification and product separation
Route.The invention uses butylene for raw material, obtains the butylene object of butylene containing 1- and 2- butylene after lightness-removing column, weight-removing column respectively
Stream, then the logistics rich in 1- butylene is obtained through isomerization reactor, butene stream obtains product through disproportionation reactor, separator
Hexene.
In the preparing hexane by disproportionating butylene method that above-mentioned patent is reported, lower, reaction that there is target product selectivities is surely
The problems such as qualitative poor.The present invention lays special stress on protecting the preparation that a kind of 1- butylene prepares hexene and catalyst for ethylene from disproportionation, passes through
Polyethylene of dispersing agent pyrrolidones is introduced, realizes the high degree of dispersion of active metal, and then inhibits double-bond isomerism and other disproportionations secondary
The progress of reaction effectively facilitates purpose product selectivity.
Summary of the invention
It is an object of the invention to develop the catalyst with base of molybdenum of a kind of efficient butylene disproportionation ethylene and hexene.
A kind of molybdenum loaded catalyst for 1- butylene self disproportionation reaction of the present invention, the catalyst is by active metal group
Divide, carrier and polyethylene of dispersing agent pyrrolidones three parts form；Wherein, the active metal component supported is the oxidation of molybdenum
Object, the main component of carrier are aluminium oxide；The load capacity of metal molybdenum element is the 1~20% of vehicle weight；For peptizaiton
Polyvinylpyrrolidone usage amount be vehicle weight 0.1%~20%.
A kind of molybdenum loaded catalyst for 1- butylene self disproportionation reaction of the present invention, the preferably load capacity of metal molybdenum element
It is 2~10% for vehicle weight.
A kind of molybdenum loaded catalyst for 1- butylene self disproportionation reaction of the present invention, is preferred for the poly- second of peptizaiton
The usage amount of alkene pyrrolidone is the 1%~10% of vehicle weight.
A kind of molybdenum loaded catalyst for 1- butylene self disproportionation reaction of the present invention, the polyethylene pyrrole for peptizaiton
The molecular weight of pyrrolidone is between 3000~100000g/mol.
The present invention is a kind of to prepare hexene/ethylene molybdenum loaded catalyst from disproportionation for 1- butylene, and used carrier is with weight
Amount percentages contain following components: 80~99.9% aluminium oxide and 0.1%~20% silica, the specific surface of carrier
Product is in 100~500m2/g。
A kind of preparation method for preparing hexene/ethylene molybdenum loaded catalyst from disproportionation for 1- butylene of the present invention, tool
Body is as follows:
(1) source Mo and dispersing agent are loaded on carrier；
(2) product for obtaining step (1) is dry at 80~120 DEG C, in moving air 500~900 DEG C of roastings 1~
4h；
The source Mo can be introduced by infusion process, ion-exchange or mechanical mixing.
Polyvinylpyrrolidone for peptizaiton mainly passes through conventional impregnation method or vacuum impregnation technology introduces.
Mainly there are ammonium molybdate, molybdenum chloride or molybdenum oxide in the source Mo.
A kind of application for preparing hexene/ethylene molybdenum loaded catalyst from disproportionation for 1- butylene of the present invention, feature
Be: reaction condition is fixed bed reactors, and reaction temperature is 50~300 DEG C, and reaction absolute pressure is 0.1~2.0MPa, weight
Amount air speed is 0.1~20h-1；The reaction raw materials are the mixture of 1- butylene or butylene and butane.
Catalyst of the present invention can make molybdenum species high degree of dispersion by introducing dispersing agent during the preparation process.The catalyst
For 1- butylene from when being disproportionated hexene processed and ethylene reaction, can effectively inhibit double-bond isomerism and other disproportionation side reactions into
Row, makes it have higher feed stock conversion and hexene/yield of ethene, meanwhile, catalyst also shows good stability.
Specific embodiment
Following embodiment will be further described the present invention, but not thereby limiting the invention.
Comparative example 1
1.14g ammonium molybdate is dissolved in 13 milliliters of water, homogeneous solution is formed.Weigh aluminium oxide (specific surface area: 250m2/
G) 10g is added in above-mentioned solution, and conventional method impregnates 30 minutes, dries 24 hours, is then put into above-mentioned sample in air
2 hours in 120 DEG C of baking ovens, sample taking-up is put into Muffle furnace later, 550 DEG C are warming up under moving air and is roasted 2 hours,
The A catalyst that Mo content is 6wt% is obtained after cooling.
Embodiment 1
0.74g ammonium molybdate and 0.5g PVP (M=10000g/mol) are dissolved in 13 milliliters of water, homogeneous solution is formed.
Weigh aluminium oxide (specific surface area: 150m2/ g) 10g, it is added in above-mentioned solution, conventional method impregnates 30 minutes, dries in air
24 hours, then above-mentioned sample is put into 100 DEG C of baking ovens 4 hours, sample taking-up is put into Muffle furnace later, it is empty in flowing
It is warming up to 550 DEG C under gas to roast 4 hours, it is 4wt% that Mo content is obtained after cooling, and PVP content is the B catalyst of 5wt%.
Embodiment 2
0.37g ammonium molybdate and 1g PVP (M=10000g/mol) are dissolved in 15 milliliters of water, homogeneous solution is formed.Claim
Take aluminium oxide (specific surface area: 220m2/ g) 10g, it is added in above-mentioned solution, vacuum impregnation 10 minutes, it is small to dry 24 in air
When, then above-mentioned sample is put into 110 DEG C of baking ovens 6 hours, sample taking-up is put into Muffle furnace later, under moving air
It is warming up to 500 DEG C to roast 6 hours, it is 2wt% that Mo content is obtained after cooling, and PVP content is the C catalyst of 10wt%.
Embodiment 3
2.29g molybdenum chloride (purity 99.5%) and 0.3g PVP (M=8000g/mol) are dissolved in 18 milliliters of water,
Form homogeneous solution.Weigh aluminium oxide (specific surface area: 230m2/ g) 10g, it is added in above-mentioned solution, conventional method impregnates 30 minutes,
It dries in air 24 hours, then above-mentioned sample is put into 140 DEG C of baking ovens 4 hours, sample taking-up is put into Muffle later
In furnace, it is warming up to 750 DEG C under moving air and roasts 2 hours, it is 8wt% that Mo content is obtained after cooling, and PVP content is
The D catalyst of 1wt%.
Embodiment 4
1.5g PVP (M=8000g/mol) is dissolved in 18 milliliters of water, homogeneous solution is formed.It weighs aluminium oxide and (compares table
Area: 280m2/ g) 10g and molybdenum oxide 1.5g (purity 99.5%), after mechanical mixture is uniform, it is added in above-mentioned solution, it is conventional
Method impregnates 30 minutes, dries 24 hours, is then put into above-mentioned sample in 80 DEG C of baking ovens 10 hours, later by sample in air
Taking-up is put into Muffle furnace, and 500 DEG C are warming up under moving air and is roasted 6 hours, and it is 10wt% that Mo content is obtained after cooling,
PVP content is the E catalyst of 20wt%.
Embodiment 5
2.79g ammonium molybdate and 1g PVP (M=58000g/mol) are dissolved in 15 milliliters of water, homogeneous solution is formed.Claim
Take aluminium oxide (specific surface area: 260m2/ g) 10g, it is added in above-mentioned solution, vacuum impregnation 30 minutes, it is small to dry 24 in air
When, then above-mentioned sample is put into 120 DEG C of baking ovens 4 hours, sample taking-up is put into Muffle furnace later, under moving air
It is warming up to 800 DEG C to roast 2 hours, it is 20wt% that Mo content is obtained after cooling, and PVP content is the F catalyst of 10wt%.
Comparative example 1 and Examples 1 to 5 reaction evaluating:
The reactivity worth evaluation of catalyst carries out on conventional fixed bed reactors, reactor inside diameter 10mm, length
For 35cm, catalyst loading 3g.Catalyst is in N22h is pre-processed at lower 500 DEG C of atmosphere, is cooled to reaction temperature later.Raw material
Mass space velocity is 4h-1, product uses Al after reaction2O3The Agilent-7890B gas-chromatography on-line analysis of-plot column, reaction
Evaluation result is as shown in table 1.Found out by table 1: compared with comparative example A, introducing polyethylene of dispersing agent pyrrolidones in the catalyst
Afterwards, the selectivity of purpose product ethylene and hexene is improved, meanwhile, the reaction stability of catalyst also makes moderate progress.
The evaluation of 1 catalyst reaction performance of table
Above-described embodiment is part preferred embodiment, is not to limit the present invention.As long as actually meeting invention
The condition that content part illustrates can realize the present invention, and therefore, the scope of the present invention is subject to the claim applied.
Claims (10)
1. a kind of molybdenum loaded catalyst for 1- butylene self disproportionation reaction, it is characterised in that: the catalyst is by active metal
Component, carrier and polyethylene of dispersing agent pyrrolidones three parts composition；Wherein, the active metal component supported is the oxidation of molybdenum
Object, the main component of carrier are aluminium oxide；The load capacity of metal molybdenum element is the 1~20% of vehicle weight；For peptizaiton
Polyvinylpyrrolidone usage amount be vehicle weight 0.1~20%.
2. according to the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 1, it is characterised in that: preferred gold
The load capacity for belonging to molybdenum element is the 2~10% of vehicle weight.
3. according to the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 1, it is characterised in that: preferably use
In peptizaiton polyvinylpyrrolidone usage amount be vehicle weight 1~10%.
4. according to the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 1, it is characterised in that: for dividing
The molecular weight of the polyvinylpyrrolidone of effect is dissipated between 3000~100000g/mol.
5. according to the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 1, it is characterised in that: load used
Body contains following components by weight percentage: 80~99.9% aluminium oxide and 0.1%~20% silica, carrier
Specific surface area is in 100~500m2/g。
6. according to the preparation method for the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 1, feature
It is that specific step is as follows:
(1) source Mo and dispersing agent are loaded on carrier；
(2) product for obtaining step (1) is dry at 80~120 DEG C, 500~900 DEG C of 1~4h of roasting in moving air.
7. according to the preparation method for the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 6, feature
Be: the source Mo can be introduced by infusion process, ion-exchange or mechanical mixing.
8. according to the preparation method for the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 6, feature
Be: dispersing agent mainly passes through conventional impregnation method or vacuum impregnation technology introduces.
9. according to the preparation method for the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 6, feature
Be: the source Mo is ammonium molybdate, molybdenum chloride or molybdenum oxide.
10. according to the application for the molybdenum loaded catalyst for being used for 1- butylene self disproportionation reaction described in claim 1, feature exists
In: the reaction raw materials are the mixture of 1- butylene or butylene and butane；Reaction condition is fixed bed reactors, reaction temperature
It is 50~300 DEG C, reaction absolute pressure is 0.1~2.0MPa, and weight space velocity is 0.1~20h-1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113385208A (en) * | 2020-03-12 | 2021-09-14 | 中国科学院大连化学物理研究所 | Molybdenum-based catalyst and preparation method and application thereof |
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