CN102491867A - Method for preparing propylene by disproportionation of ethylene and long carbon chain olefin - Google Patents
Method for preparing propylene by disproportionation of ethylene and long carbon chain olefin Download PDFInfo
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- CN102491867A CN102491867A CN2011103805371A CN201110380537A CN102491867A CN 102491867 A CN102491867 A CN 102491867A CN 2011103805371 A CN2011103805371 A CN 2011103805371A CN 201110380537 A CN201110380537 A CN 201110380537A CN 102491867 A CN102491867 A CN 102491867A
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Abstract
The present invention relates to a method for preparing propylene by disproportionation of ethylene and a long carbon chain olefin. According to the method, ethylene and a long carbon chain olefin are adopted as raw materials, and the ethylene and the long carbon chain olefin contact a transition metal oxide-containing catalyst and/or an alkaline earth metal oxide to carry out a disproportionation reaction to generate the propylene. With the technical scheme of the present invention, the olefin disproportionation reaction is adopted to convert the long carbon chain internal olefin into the high added value propylene and other basic organic chemical engineering raw materials so as to solve the reutilization problem of the long carbon chain internal olefin generated during the olefin oligomerization process, paraffin cracking process and other processes. The method of the present invention has advantages of high long carbon chain olefin conversion rate, high propylene yield, and the like, wherein the long carbon chain olefin conversion rate can be more than 90%, and the propylene selectivity can be more than 50%.
Description
Technical field
The present invention relates to a kind of preparation method of propylene, relate in particular to the method for a kind of ethene and long carbochain preparing propylene through olefin disproportionation, belong to the Organic Chemicals production technical field.
Background technology
Terminal olefin is to develop very a kind of rapidly important Organic Chemicals in recent decades, has purposes widely.The terminal olefin of low carbon chain, particularly 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene mainly are used as the comonomer of synthesizing linear low-density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE).1-decene mainly is used as the raw material of the base oil of synthetic senior lubricant.The terminal olefin of high carbon chain is mainly as synthetic detergent, softening agent, tensio-active agent, lubricating oil and auxiliary agent etc.At present the compound method of terminal olefin mainly contains wax cracking method, dehydrating alkanes method and ethylene oligomerization method etc., but these technologies all can by-product a certain amount of be main long carbochain alkene with the nonterminal olefin, these nonterminal olefins do not have the application approach of getting well.How to make good use of this part nonterminal olefin, increase its added value, improve the performance of enterprises, become the problem that petroleum chemical enterprise presses for solution.
EP0136377 has reported a kind of with C
13-C
14Mixtures of internal olefins (optional C
9-C
24Nonterminal olefin or its mixture) be raw material, adopting boron trifluoride-propyl carbinol is the oligomerisation of catalyst nonterminal olefin, produces the technology of synthetic lubricant base oil, 99 ℃ of viscosity: 3-5mm of product
2/ s, viscosity index: more than 110, pour point:＜-45 ℃.
EP1104747 has reported a kind of with C
13-C
14Mixtures of internal olefins is a raw material, the technology of using boron trifluoride-phosphoric acid to produce synthetic lubricant base oil as the oligomerisation of catalyst nonterminal olefin, 100 ℃ of viscosity: 5-7mm of product
2/ s, viscosity index: more than 120, pour point: minimum reaching-79 ℃.
US4167534 has reported a kind of with anhydrous AlCl
3Catalysis is from the C of Pacol-Olex technology
11-C
14Mixtures of internal olefins (optional C
9-C
18Nonterminal olefin or its mixture) oligomerisation produces the technology of synthetic lubricant base oil, and product is mainly dimer and tripolymer, and viscosity index is more than 100, below the pour point-40 ℃.
In the related technology of above-mentioned patent, the synthetic lubricant base oil of producing with the nonterminal olefin oligomerisation usually slightly is inferior to the synthetic lubricant base oil with terminal olefin oligomerisation production on viscosity index and low-temperature fluidity, and has only C
12-C
20The nonterminal olefin oligomerisation base oil performance of producing more excellent, and C
8-C
12The base oil produced of nonterminal olefin bigger than terminal olefin gap on performance of same carbon number.
Propylene also is one of a kind of important Organic Chemicals, is mainly used in synthetic Vestolen PP 7052, isopropyl benzene, vinylformic acid etc., wherein, produces Vestolen PP 7052 and accounts for more than 60% of propylene demand.In recent years, increasing to the demand of propylene along with the development of polypropylene industrial, the growth rate of demand of propylene has surpassed ethene, becomes one of the fastest industrial chemicals of demand growth.
Olefin metathesis is olefin metathesis or olefin metathesis reactions again, can superfluous, that added value is lower relatively olefin product be converted into the olefin product of high added value through disproportionation reaction.In the technical study to propylene enhancing, olefin metathesis technology is because its energy consumption is low, and can with most of process integrations, since invention, be subjected to increasing people's attention.
US4472522 and US4503280 have reported a kind of technology of ethylene oligomerization production terminal olefin respectively.The maximum characteristics of this technology are introduced disproportionation processes exactly after ethylene oligomerization is produced terminal olefin; Isolated high carbon chain alkene is at first passed through isomerizing; Carry out disproportionation reaction with 1-butylene then, thereby improve the utilization ratio of ethene, ethene at utmost is converted into useful olefin product.
US5300718 has reported the technology of a kind of ethene and 2-butylene disproportionation system propylene, and the catalyzer that uses is MgO and WO
3/ SiO
2Mixed bed.
WO00014038 has reported a kind of method of preparing propylene by butene disproportionation.With 1-butylene, 2-butylene or its mixture is raw material, WO
3/ SiO
2Or Cs
+, PO
4 3-The WO of modification
3/ SiO
2Be catalyzer,, carry out disproportionation reaction under the condition of pressure 1atm, thereby produce propylene at temperature of reaction 500-550 ℃.
The related technology of above-mentioned document all is the alkene that carries out carbochain in the middle of the disproportionation reaction system with butylene and ethene or high carbon chain alkene, and ethene does not appear in the newspapers with the technology of long carbochain nonterminal olefin disproportionation system propylene as yet.
Summary of the invention
For addressing the above problem; The object of the present invention is to provide a kind of working method of propylene; Is raw material with ethene with long carbochain nonterminal olefin, obtains the basic Organic Chemicals such as propylene of high added value through disproportionation reaction, and what solve long carbochain nonterminal olefin utilizes problem again.
For achieving the above object; The invention provides the method for a kind of ethene and long carbochain preparing propylene through olefin disproportionation; It is to be raw material with ethene with long carbochain alkene, raw material is contacted with catalyzer that contains transition metal oxide and/or alkaline earth metal oxide and the method for disproportionation reaction production propylene takes place.
Working method provided by the present invention adopts the method for olefin metathesis will be worth low long carbochain nonterminal olefin and is converted into costly short carbon chain alkene (particularly propylene), thereby has improved its added value, improves the performance of enterprises.
The working method of aforesaid propylene provided by the present invention preferably includes following concrete steps:
A, ethene and long carbochain alkene are fed in the fixed-bed reactor, it is contacted with catalyzer that contains transition metal oxide and/or alkaline earth metal oxide and disproportionation reaction takes place;
B, reaction product is carried out rectifying, tell ethene, propylene and other carbochain alkene except that ethylene, propylene, make unreacted ethene and other carbochain alkene Returning reactor again, recycle.
In aforementioned production method, can carry out according to the common mode that adopts in this area the rectifying of reaction product.
In aforementioned production method, the long carbochain nonterminal olefin that is adopted can be to produce in the technological processs such as wax cracking, dehydrating alkanes, acetate oligomerization system terminal olefin, also can be the long carbochain alkene of other low value, and preferably, above-mentioned long carbochain alkene is C
6-C
18Alkene or its mixture.
In aforementioned production method, preferably, the catalyzer that contains transition metal oxide that is adopted is tungsten-based catalyst and/or catalyst with base of molybdenum etc., and the alkaline earth metal oxide that is adopted is a Natural manganese dioxide etc.More preferably, above-mentioned tungsten-based catalyst is WO
3/ SiO
2, wherein, SiO
2Be carrier, above-mentioned catalyst with base of molybdenum is MoO
3/ Al
2O
3, wherein, Al
2O
3Be carrier.According to concrete technical scheme of the present invention, at WO
3/ SiO
2In, WO
3Content may be controlled to 5-25wt%; At MoO
3/ Al
2O
3In, MoO
3Content may be controlled to 4-30wt%.
In aforementioned production method, preferably, alkaline earth metal oxide may be controlled to 0-5 with the part by weight that contains the catalyzer of transition metal oxide: 1, and 0.3-3 more preferably: 1.
In aforementioned production method, preferably, ethene may be controlled to 2-25 with the mol ratio of long carbochain alkene: 1, and 3-20 more preferably: 1; When long carbochain alkene is the mixture of multiple alkene, calculate with the amount of substance sum of various alkene.
In aforementioned production method, preferably, the temperature of reaction of disproportionation reaction may be controlled to 100-550 ℃ (being preferably 150-500 ℃), and reaction pressure may be controlled to 0.1-5MPa (being preferably 0.1-3MPa), and the reaction weight hourly space velocity may be controlled to 1-20 hour
-1(be preferably 1-12 hour
-1).
In aforementioned production method, preferably, with WO
3/ SiO
2During for catalyzer, the temperature of reaction of disproportionation reaction may be controlled to 300-500 ℃, and reaction pressure may be controlled to 0.1-5MPa, and the reaction weight hourly space velocity may be controlled to 1-20 hour
-1With MoO
3/ Al
2O
3During for catalyzer, the temperature of reaction of disproportionation reaction may be controlled to 100-350 ℃, and reaction pressure is 0.1-5MPa, and the reaction weight hourly space velocity is 1-20 hour
-1
Ethene provided by the present invention can carry out according to flow process illustrated in figures 1 and 2 with the method for long carbochain preparing propylene through olefin disproportionation, and wherein, flow process shown in Figure 1 comprises following concrete steps:
1, ethene and long carbochain alkene are fed in the fixed-bed reactor, it is contacted with catalyzer that contains transition metal oxide and/or alkaline earth metal oxide and disproportionation reaction takes place;
2, reaction product being carried out conventional rectification separates.Make reaction product get into first rectifying tower, isolate long carbochain alkene and it is got back in the reactor drum recycle, make the overhead product of first rectifying tower get into second rectifying tower, tell ethene and propylene, unreacted ethene Returning reactor is recycled.
Flow process shown in Figure 2 comprises following concrete steps:
1, ethene and long carbochain alkene are fed in the fixed-bed reactor, it is contacted with catalyzer that contains transition metal oxide and/or alkaline earth metal oxide and disproportionation reaction takes place;
2, reaction product being carried out conventional rectification separates.Make reaction product get into first rectifying tower, isolate ethene and it is got back in the reactor drum recycle, make the low overhead product of tower of first rectifying tower get into second rectifying tower, tell propylene, other long carbochain alkene Returning reactors of the low distilled of tower are recycled.
The nonterminal olefin that technical scheme provided by the present invention will be grown carbochain through olefin dismutation reaction is converted into the basic Organic Chemicals such as propylene of high added value, and what solved the long carbochain nonterminal olefin that produces in the technological processs such as olefin oligomerization, wax cracking utilizes problem again.Method with ethene and long carbochain olefin production propylene provided by the present invention has the high and propene yield advantages of higher of long carbochain olefin conversion, and long carbochain conversion of olefines rate can reach more than 90%, and the propylene selectivity can reach more than 50%.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for ethene provided by the present invention and long carbochain preparing propylene through olefin disproportionation;
Fig. 2 is the synoptic diagram of another flow process of ethene provided by the present invention and the method for growing the carbochain preparing propylene through olefin disproportionation.
Embodiment
To understand in order technical characterictic of the present invention, purpose and beneficial effect being had more clearly, technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as qualification at present practical range of the present invention.
The by product that the long carbochain alkene that the embodiment of the invention adopted is the superimposed synthetic 1-hexene of ethene, the composition of this long carbochain alkene is as shown in table 1, and the staple of raw material is a decene.The technical process of being adopted among the embodiment can be any one in the technical process illustrated in figures 1 and 2.
The composition of the long carbochain alkene of table 1
| The alkene kind | Form (weight %) |
| Hexene | 3.47 |
| Octene | 5.60 |
| Decene | 90.01 |
| Laurylene | 0.92 |
Embodiment 1-4
The method that embodiment 1-4 provides a kind of ethene and long carbochain alkene to produce propylene through disproportionation reaction respectively, wherein, these four embodiment adopt different ethene and long carbochain alkene proportioning respectively, and concrete steps are following:
Take by weighing 0.38 gram WO
3/ SiO
2Catalyzer is (in the gross weight of this catalyzer, WO
3Content be 8wt%) and 0.38 gram MgO pack into after mixing in the fixed-bed reactor; In nitrogen atmosphere, being warmed up to 550 ℃ handled 1 hour; Cool to 420 ℃ then, feeding hydrogen and the flow that flow is 4 ml/min simultaneously is the nitrogen of 36 ml/min, handles 30 minutes at 420 ℃;
Be cooled to 400 ℃ (being the disproportionation reaction temperature), feed ethene and long carbochain olefin feedstock, make itself and WO
3/ SiO
2Catalyzer contacts with MgO and carries out disproportionation reaction, produces propylene, and wherein, the pressure of disproportionation reaction is 3MPa, and the reaction weight hourly space velocity is 6 hours
-1, ethene was respectively 3: 1,7: 1,10: 1,15: 1 with long carbochain alkene (integral molar quantities of four kinds of alkene) mol ratio.
Analyzed by gas chromatographic analysis behind the gas-phase product of collection disproportionation reaction and the liquid product, concrete analytical results is as shown in table 2.
Disproportionation reaction product analysis result under ethene that table 2 is different and the long carbochain olefin molar ratio condition
Embodiment 5-8
The method that embodiment 5-8 provides a kind of ethene and long carbochain alkene to produce propylene through disproportionation reaction respectively, wherein, these four embodiment adopt different disproportionation reaction temperature respectively, and concrete steps are following:
With 0.19 gram WO
3/ SiO
2Catalyzer is (in the gross weight of this catalyzer, WO
3Content be 8wt%) and 0.19 the gram MgO carry out catalyst loading and pre-treatment by the step shown in the embodiment 1;
Be cooled to disproportionation reaction temperature (the disproportionation reaction temperature of four embodiment is respectively 360 ℃, 400 ℃, 430 ℃, 460 ℃), feed ethene and long carbochain alkene, make itself and WO
3/ SiO
2Catalyzer contacts with MgO and carries out disproportionation reaction, produces propylene, and wherein, the pressure of disproportionation reaction is 3MPa, and the reaction weight hourly space velocity is 12 hours
-1, ethene was respectively 10: 1 with long carbochain alkene (integral molar quantities of four kinds of alkene) mol ratio.
Analyzed by gas chromatographic analysis behind the gas-phase product of collection disproportionation reaction and the liquid product, concrete analytical results is as shown in table 3.
Disproportionation reaction product analysis result under the different disproportionation reaction temperature of table 3
Embodiment 9-12
The method that embodiment 9-12 provides a kind of ethene and long carbochain alkene to produce propylene through disproportionation reaction respectively, wherein, these four embodiment adopt different disproportionation reaction pressure respectively, and concrete steps are following:
With 0.19 gram WO
3/ SiO
2Catalyzer is (in the gross weight of this catalyzer, WO
3Content be 8wt%) and 0.19 the gram MgO carry out catalyst loading and pre-treatment by the step shown in the embodiment 5-8;
Be cooled to 400 ℃ (being the disproportionation reaction temperature), feed ethene and long carbochain alkene, make itself and WO
3/ SiO
2Catalyzer contacts with MgO and carries out disproportionation reaction, produces propylene, and wherein, the pressure of the disproportionation reaction among four embodiment is respectively 1MPa, 2MPa, 3MPa, 4MPa, and the reaction weight hourly space velocity is 12 hours
-1, ethene was respectively 10: 1 with long carbochain alkene (integral molar quantities of four kinds of alkene) mol ratio.
Analyzed by gas chromatographic analysis behind the gas-phase product of collection disproportionation reaction and the liquid product, concrete analytical results is as shown in table 4.
Disproportionation reaction product analysis result under the different disproportionation reaction pressure of table 4
Embodiment 13-15
The method that embodiment 13-15 provides a kind of ethene and long carbochain alkene to produce propylene through disproportionation reaction respectively, wherein, these three embodiment adopt different disproportionation reaction weight hourly space velocitys respectively, and concrete steps are following:
Step by shown in the embodiment 5-8 is carried out catalyst loading and pre-treatment;
Be cooled to 400 ℃ (being the disproportionation reaction temperature), feed ethene and long carbochain alkene, make itself and WO
3/ SiO
2Catalyzer contacts with MgO and carries out disproportionation reaction, produces propylene, and wherein, the pressure of disproportionation reaction is 2MPa, and the reaction weight hourly space velocity of three embodiment was respectively 1 hour
-1, 3 hours
-1, 6 hours
-1, ethene was respectively 10: 1 with long carbochain alkene (integral molar quantities of four kinds of alkene) mol ratio.
Analyzed by gas chromatographic analysis behind the gas-phase product of collection disproportionation reaction and the liquid product, concrete analytical results is as shown in table 5.
Disproportionation reaction product analysis result under the different disproportionation reaction weight hourly space velocitys of table 5
Embodiment 16-18
The method that embodiment 16-18 provides a kind of ethene and long carbochain alkene to produce propylene through disproportionation reaction respectively, wherein, these three embodiment adopt different oxidation magnesium and catalyst weight ratio respectively, and concrete steps are following:
With WO
3/ SiO
2Catalyzer and MgO carry out catalyst loading and pre-treatment by the step shown in the embodiment 1-4, wherein, and MgO and WO
3/ SiO
2The weight ratio of catalyzer was respectively 3: 1,1: 1,1: 3;
Be cooled to 400 ℃ (being the disproportionation reaction temperature), feed ethene and long carbochain alkene, make itself and WO
3/ SiO
2Catalyzer contacts with MgO and carries out disproportionation reaction, produces propylene, and wherein, the pressure of disproportionation reaction is 2MPa, and the reaction weight hourly space velocity is 6 hours
-1, ethene was respectively 10: 1 with long carbochain alkene (integral molar quantities of four kinds of alkene) mol ratio.
Analyzed by gas chromatographic analysis behind the gas-phase product of collection disproportionation reaction and the liquid product, concrete analytical results is as shown in table 6.
Disproportionation reaction product analysis result under table 6 different oxidation magnesium compares with catalyst weight
Embodiment 19
Implement 19 a kind of ethene and the method for long carbochain alkene through disproportionation reaction production propylene are provided respectively, its concrete steps are following:
With MoO
3/ Al
2O
3Catalyzer (MoO
3Content be 12wt%) in the fixed-bed reactor of packing into, in nitrogen atmosphere, be warmed up to 550 ℃ and handled 1 hour, be cooled to 200 ℃ (being the disproportionation reaction temperature) then, feed ethene and long carbochain alkene, make itself and MoO
3/ Al
2O
3Disproportionation reaction is carried out in the catalyzer contact, produces propylene, and wherein, the pressure of disproportionation reaction is 1MPa, and the reaction weight hourly space velocity is 2 hours
-1, ethene is 10: 1 with long carbochain alkene (integral molar quantities of four kinds of alkene) mol ratio.
Analyze by gas chromatographic analysis behind the gas-phase product of collection disproportionation reaction and the liquid product; Concrete analytical results is: the decene transformation efficiency is 87.23mol%; Conversion of ethylene is 25.32mol%; Propylene 64.5mol% in the product, hexene-nonene 9.12mol%, carbon 11 and above alkene are 0.52mol%.
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; And be not used in qualification protection scope of the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the method for an ethene and long carbochain preparing propylene through olefin disproportionation, it is to be raw material with ethene with long carbochain alkene, raw material is contacted with catalyzer that contains transition metal oxide and/or alkaline earth metal oxide and the method for disproportionation reaction production propylene takes place.
2. method according to claim 1, wherein, this method may further comprise the steps:
A, ethene and long carbochain alkene are fed in the fixed-bed reactor, it is contacted with catalyzer that contains transition metal oxide and/or alkaline earth metal oxide and disproportionation reaction takes place;
B, reaction product is carried out conventional rectification separate, tell ethene, propylene and other carbochain alkene except that ethylene, propylene, make unreacted ethene and other carbochain alkene Returning reactor again, recycle.
3. method according to claim 1 and 2, wherein, said long carbochain alkene is C
6-C
18Alkene or its mixture.
4. method according to claim 1 and 2, wherein, the said catalyzer that contains transition metal oxide is tungsten-based catalyst and/or catalyst with base of molybdenum, said alkaline earth metal oxide is a Natural manganese dioxide.
5. method according to claim 4, wherein, said tungsten-based catalyst is WO
3/ SiO
2, said catalyst with base of molybdenum is MoO
3/ Al
2O
3
6. method according to claim 5, wherein, at said WO
3/ SiO
2In, WO
3Content be 5-25wt%; At said MoO
3/ Al
2O
3In, MoO
3Content be 4-30wt%.
7. according to claim 1,2 or 4 described methods, wherein, said alkaline earth metal oxide is 0-5 with the part by weight that contains the catalyzer of transition metal oxide: 1, be preferably 0.3-3: 1.
8. method according to claim 1 and 2, wherein, said ethene is 2-25 with the mol ratio of long carbochain alkene: 1, be preferably 3-20: 1.
9. method according to claim 1 and 2, wherein, the temperature of reaction of said disproportionation reaction is 100-550 ℃, and reaction pressure is 0.1-5MPa, and the reaction weight hourly space velocity is 1-20 hour
-1
10. according to claim 5 or 9 described methods, wherein, with said WO
3/ SiO
2During for catalyzer, the temperature of reaction of said disproportionation reaction is 300-500 ℃, and reaction pressure is 0.1-5MPa, and the reaction weight hourly space velocity is 1-20 hour
-1With said MoO
3/ Al
2O
3During for catalyzer, the temperature of reaction of said disproportionation reaction is 100-350 ℃, and reaction pressure is 0.1-5MPa, and the reaction weight hourly space velocity is 1-20 hour
-1
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| CN201110380537.1A CN102491867B (en) | 2011-11-25 | 2011-11-25 | Method for preparing propylene by disproportionation of ethylene and long carbon chain olefin |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300718A (en) * | 1988-09-19 | 1994-04-05 | Lyondell Petrochemical Company | Olefin conversion process |
| CN1915510A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through olefin disproportionation |
| CN102040444A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing propylene by butylene and ethene |
| CN102125871A (en) * | 2011-01-14 | 2011-07-20 | 中国石油大学(北京) | Catalyst for olefin metathesis as well as preparation method and application thereof |
-
2011
- 2011-11-25 CN CN201110380537.1A patent/CN102491867B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300718A (en) * | 1988-09-19 | 1994-04-05 | Lyondell Petrochemical Company | Olefin conversion process |
| CN1915510A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through olefin disproportionation |
| CN102040444A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing propylene by butylene and ethene |
| CN102125871A (en) * | 2011-01-14 | 2011-07-20 | 中国石油大学(北京) | Catalyst for olefin metathesis as well as preparation method and application thereof |
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