CN104447168B - A kind of method for producing 1 hexene coproduction heptene and octene - Google Patents
A kind of method for producing 1 hexene coproduction heptene and octene Download PDFInfo
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- CN104447168B CN104447168B CN201310430004.9A CN201310430004A CN104447168B CN 104447168 B CN104447168 B CN 104447168B CN 201310430004 A CN201310430004 A CN 201310430004A CN 104447168 B CN104447168 B CN 104447168B
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Abstract
The invention discloses a kind of method for producing 1 hexene co-production heptene and octene, wherein ethene and propylene carries out the product that trimerization reaction obtains including 1 hexene, heptene and octene in the presence of catalyst system, wherein the catalyst system includes following components：A contains chromium compound, and formula is CrRm, and wherein R is selected from inorganic or organic group, 0≤m≤6；B ligands, selected from heterocyclic compound and containing Phosphine ligands；C organo-aluminum compounds.According to the method that the present invention is provided, the heptene and octene product of coproduction high added value while can preparing 1 hexene by ethene and propylene trimerization, application prospect are extensive.
Description
Technical field
The present invention relates to a kind of method for preparing alpha-olefin, in particular, it is related to a kind of ethene and propylene trimerization to prepare
1- hexene coproduction heptene, the method for octene.
Background technology
1- hexenes, heptene and octene are highly useful Organic Chemicals, are widely used.Alkene is important basic to 1-
Organic Chemicals, shows, 1- hexenes have obvious effect to the performance for improving device polyolefin by research and development.It is mainly used as
Produce the comonomer and some fine chemicals raw materials of high-quality polyethylene.Heptene and octene are mainly used in production synthesis profit
Lubricant base is oily and as the raw material through carbonylation synthesis isooctanol, can also be hydrogenated into the modulation component of high-knock rating gasoline,
Added value of product can be improved, application prospect is extensive.
After union carbide corporation reports and prepares 1- hexene methods using chromium-based catalysts catalysis ethene, have both at home and abroad more
Patent reports using chromium-based catalysts the method to prepare 1- hexenes, wherein Philips Corporate and Sinopec Beijing chemical industry
1- hexenes production technology all successful commercializations of Yanshan Mountain branch of research institute exploitation, its technological process is simple, advanced technology, institute
The catalyst system for using has active and excellent selectivity higher.But most products of above method production are 1-
The product of carbon 6 such as hexene, 2- hexenes, 3- hexenes, can hardly generate the heptene and octene of same high added value.
The content of the invention
It is an object of the invention to provide a kind of method for producing 1- hexene coproduction heptene, octene.There is provided using the present invention
Method, it is impossible to 1- hexenes can be produced, while the heptene and octene of high added value can also be produced.
According to the method that the present invention is provided, there is provided a kind of ethylene, propylene trimerization prepares 1- hexene co-production heptene and octene
Method, wherein ethene and the propylene trimerization in the presence of catalyst system obtains including the product of 1- hexenes, heptene and octene,
Wherein described catalyst system includes following components：
A contains chromium compound, and formula is CrRm, and wherein R is selected from inorganic and organic group, 0≤m≤6；
B ligands, selected from heterocyclic compound and containing Phosphine ligands；
C organo-aluminum compounds.
According to the method that the present invention is provided, while 1- hexenes are produced, additionally it is possible to produce the heptene of high added value and pungent
Alkene.Heptene and octene are mainly used in organic synthesis as organic synthesis raw material, can produce synthetic lubricant base oil and
Through carbonylation synthesis isooctanol, the modulation component of high-knock rating gasoline can be also hydrogenated into, application prospect is extensive.
According to the method that the present invention is provided, component a, b, the mol ratio of c are 1 in the catalyst system:1-30:1-500,
Preferably 1:1-5:50-200.In described molar ratio range, feed ethylene and propylene are selected under catalyst action
Property trimerization, in product be mainly 1- hexene products, also simultaneously generate heptene and octene, product it is widely used.
According to the method that the present invention is provided, component a in the catalyst system containing chromium compound, can be unification
The mixture of compound, or various chromium compounds.The valence state of chromium is 0-6 valencys in the component a.Specific R group is for example
It is the group containing carbonyl and alkyl.Inorganic group can be halogen ion, sulfate ion or oxonium ion.Organic group can contain 1-
20 carbon atoms, preferably 1-10 can be selected from alkyl, cycloalkyl, monocyclic and polyaromatic, alkoxy, ester group, ketone group etc..Its
In, the alkyl can be straight or branched.
In one specific embodiment of the method provided according to the present invention, preferred m is 0 to 3 in the component a.It is preferred that institute
State and be selected from tetrahydrofuran chromium chloride, chromium chloride, chromium acetylacetonate, isooctyl acid chromium and three (tetrahydrofuran) tri-chlorinations containing chromium compound
Chromium.
In one specific embodiment of the method provided according to the present invention, preferably described ligand can be heterocyclic compound
Thing, its formula is ERn, and E is heterocycle, and R is selected from substituted or unsubstituted straight or branched alkyl, cycloalkyl and aromatic alkyl, n
It is 1-20.The preferred five-ring heterocycles of E, more preferably furans, thiophene, pyrroles.The preferred straight chained alkyls of R, more preferably methyl, ethyl, propyl group.
N preferred 1-10, more preferably 1-6.
In a preferred embodiment, the ligand is diphosphine ligand, and its formula is R1P-R2-PR3, R1And R3It is identical
Or it is different, selected from C1-C20Substituted or unsubstituted alkyl, cycloalkyl, alkaryl and aralkyl, preferably C1-C10Alkyl, ring
Alkyl, alkaryl and aralkyl, such as phenyl, tolyl；R2It is C1-C10Alkylidene or alkyl tert amido, preferably C1-C6
Alkylidene or alkyl tert amido, such as methylene, ethylidene, isopropyl tertiary amine groups.
In the present invention, the organo-aluminum compound is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound.In the present invention, the alkane
The formula of base aluminium compound is AlRnXm, wherein R is each independently straight or branched C1-C8Alkyl；X is respectively halogen, preferably
Chlorine or bromine；N is 1~3 integer, and m is 0~2 integer, and m+n is equal to 3；As trimethyl aluminium, triethyl aluminum, tri-propyl aluminum,
Triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride.In the present invention, the aluminium
Oxygen alkane is C1-C4Alkylaluminoxane, wherein C1-C4Alkyl is the alkyl of straight or branched；Such as MAO, modified methyl aluminium
Oxygen alkane, ethylaluminoxane and isobutyl aluminium alkoxide.In a preferred embodiment, the organoaluminium compound is selected from front three
Base aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, aluminium methyl
Oxygen alkane, ethylaluminoxane and modified methylaluminoxane, are preferably selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and aluminium methyl
Oxygen alkane.
According to the method that the present invention is provided, the reaction temperature of the trimerization reaction is 0~200 DEG C, reaction pressure is 0.5~
20MPa, the reaction time is 0.1~5h.Preferably, the reaction temperature of the trimerization reaction is 50~150 DEG C, and reaction pressure is 2
~8MPa, the reaction time is 0.2~2h.
The consumption of the catalyst system in the solution can be added according to device, production scale etc..There is provided according to the present invention
Method a specific embodiment in, the trimerization reaction is carried out in varsol, the consumption of the catalyst system with
Chromium in component a is calculated as 0.01~10.0mmol/L.Varsol commonly used in the prior art is used equally in the present invention.
In one specific embodiment of the method provided according to the present invention, ethene and propylene molar ratio are 1:0.1-1:2,1:
0.2~1:1.In the molar ratio range, be conducive to obtaining the heptene and octene of higher amount.
According to being actually needed for the inventive method, the reaction in the present invention can be batch (-type), semi continuous or continous way.
According to the method that the present invention is provided, coproduction is high additional while can preparing 1- hexenes by ethene and propylene trimerization
The heptene and octene product of value.Alkene is important fine chemical material to 1-, and used as comonomer, 1- hexenes are to improving polyolefin
Performance have an obvious effect, extensively using and production high-quality polyethylene comonomer and some fine chemicals raw materials.Heptan
Alkene and octene are mainly used in production synthetic lubricant base oil and as the raw material through carbonylation synthesis isooctanol, can also add
Hydrogen can improve added value of product into the modulation component of high-knock rating gasoline, and application prospect is extensive.By controlling three kinds in catalyst
The mol ratio of component, can also adjust the 1- hexenes and heptene and the ratio of octene for obtaining.According to the method that the present invention is provided,
It is with a wide range of applications.
Specific embodiment
The present invention is further described with reference to embodiment, but does not constitute any limitation of the invention.
Embodiment 1
There are addition 80ml n-heptane solutions in the reactor of mechanical stirring device to ethene protection lower band, start to warm up heating
To 100 DEG C, the n-heptane solution of the catalyst system that will be prepared is rapidly added in kettle, and the consumption of catalyst system is with chromium
It is calculated as 0.1mmol/L（The cumulative volume of solution in kettle）, the mol ratio a of three kinds of components of addition：b：c（That is isooctyl acid chromium:2,5- bis-
Methylpyrrole:Triethyl aluminum）It is 1:5:80, after stirring 3min, to being passed through mol ratio 1 in kettle:0.5 ethylene/propene mixed gas,
Pressure starts initiation reaction, 100 DEG C of controlling reaction temperature, reaction time 0.5h to 3.0MPa.Requirement is reached between when reacted
Afterwards, jacket water (J.W.) is cooled to normal temperature, stops stirring, measures liquid phase respectively, sampling analysis, and gas, liquid product is by gas-chromatography
Analysis, contains various heptene and octene component in product.According to products weight calculate catalyst efficiency be 223184g products/
GCr.h, wherein 1- hexenes, heptene, the selectivity of octene is 3.32%, 2.16%.Data are shown in Table 1.
Embodiment 2
With embodiment 1, difference is that the mol ratio of ethylene/propene mixed gas is 1:0.25, pressure is
5.0MPa.It is 286283g products/gCr.h, wherein heptene to calculate catalyst efficiency according to products weight, and the selectivity of octene is
2.36%, 1.58%.Data are shown in Table 1.
Embodiment 3
With embodiment 1, difference is that the consumption of catalyst is calculated as 0.2mmol/L with chromium, and pressure is
4.0MPa.It is 259357g products/gCr.h, wherein heptene to calculate catalyst efficiency according to products weight, and the selectivity of octene is
3.87%, 2.35%.Data are shown in Table 1.
Embodiment 4
With embodiment 1, difference is, three kinds of mol ratio a of component:b:C is 1:5:200.According to products weight meter
Calculation catalyst efficiency is 293862g products/gCr.h, wherein heptene, and the selectivity of octene is 5.25%, 3.86%.Data are shown in Table 1.
Embodiment 5
With embodiment 1, difference is that the mol ratio of ethylene/propene mixed gas is 1:1, pressure is 4.0MPa.Root
It is 193625g products/gCr.h, wherein heptene to calculate catalyst efficiency according to products weight, and the selectivity of octene is 4.58%,
2.62%.Data are shown in Table 1.
Embodiment 6
With embodiment 1, difference is, three kinds of mol ratio a of component：b：c（That is tetrahydrofuran chromium chloride:2,5- bis-
Methylpyrrole:Triethyl aluminum）It is 1:5:200.It is 274763g products/gCr.h to calculate catalyst efficiency according to products weight, its
Middle heptene, the selectivity of octene is 5.01%, 3.47%.Data are shown in Table 1.
Embodiment 7
With embodiment 1, difference is, three kinds of mol ratio a of component：b：c（That is chromium acetylacetonate:((C6H5)2P)2NCH(CH3)2:Triethyl aluminum）It is 1:2:300.It is 52363g products/gCr.h to calculate catalyst efficiency according to products weight, its
Middle heptene, the selectivity of octene is 18.31%, 12.27%.Data are shown in Table 1.
Table 1
By table 1 it is known that the method provided according to the present invention, can obtain high added value while 1- hexenes are produced
Heptene and octene.According to the method that the present invention is provided, it is with a wide range of applications.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (14)
1. a kind of method for producing 1- hexene co-production heptene and octene, wherein ethene and propylene is in the presence of catalyst system
The product that trimerization reaction obtains including 1- hexenes, heptene and octene is carried out, wherein the catalyst system includes following components：
A contains chromium compound, and formula is CrRm, and wherein R is selected from inorganic and organic group, 0≤m≤6；
B ligands, selected from heterocyclic compound and containing Phosphine ligands；
C organo-aluminum compounds, selected from alkyl aluminum compound；
Wherein, the trimerization reaction is carried out in varsol, and the consumption of the catalyst system is in terms of the chromium in component a
It is 0.01~10.0mmol/L, ethene and propylene molar ratio are 1:0.5-1:1, component a, b in the catalyst system, c rub
You are than being 1:1-5:80-300；
Wherein, the phosphorus-containing ligand is diphosphine ligand, and its formula is R1P-R2-PR3, R1And R3It is identical or different, selected from C1-C20's
Substituted or unsubstituted alkyl, cycloalkyl and unsubstituted aryl, R2It is C1-C10Alkylidene or alkyl tert amido.
2. method according to claim 1, it is characterised in that component a, b, the mol ratio of c are in the catalyst system
1:2-5:80-200。
3. method according to claim 1, it is characterised in that m is 0 to 3 in the catalyst system；R be selected from halogen ion,
Sulfate ion, oxonium ion and C1-C20Straight or branched alkyl, cycloalkyl, monocyclic aryl, polyaromatic, alkoxy, ester
Base and ketone group.
4. method according to claim 1, it is characterised in that described to be selected from tetrahydrofuran chromium chloride, second containing chromium compound
Acyl acetone chromium, isooctyl acid chromium, chromium chloride and three (tetrahydrofuran) chromium trichlorides.
5. the method according to any one in Claims 1 to 4, it is characterised in that the ligand is heterocyclic compound,
Its formula is ER ' n, and in formula, E is heterocycle；R ' is selected from substituted or unsubstituted straight or branched alkyl, cycloalkyl and aromatics alkane
Base；N is 1-20.
6. method according to claim 5, it is characterised in that in the heterocyclic compound formula, E is five-ring heterocycles, R '
It is straight chained alkyl, n is 1-10.
7. method according to claim 5, it is characterised in that in the heterocyclic compound formula, E be furans, thiophene or
Pyrroles；R ' is methyl, ethyl or propyl group；N is 1-6.
8. the method according to any one in Claims 1 to 4, it is characterised in that the phosphorus-containing ligand general formula R1P-R2-
PR3In, R1And R3It is identical or different, selected from C1-C10Substituted or unsubstituted alkyl, cycloalkyl and unsubstituted aryl；R2For
C1-C6Alkylidene or alkyl tert amido.
9. the method according to any one in Claims 1 to 4, it is characterised in that the formula of the alkyl aluminum compound
It is AlRnXm, wherein R is each independently straight or branched C1-C8Alkyl；X is respectively halogen；N is 1~3 integer, m is 0~
2 integer, and m+n is equal to 3.
10. method according to claim 9, it is characterised in that in the formula of the alkyl aluminum compound, X is chlorine or bromine.
11. methods according to claim 9, it is characterised in that the alkyl aluminum compound is selected from trimethyl aluminium, three second
Base aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride and ethyl aluminum dichloride.
12. methods according to claim 9, it is characterised in that the alkyl aluminum compound is selected from trimethyl aluminium, triethyl aluminum
And triisobutyl aluminium.
13. method according to any one in Claims 1 to 4, it is characterised in that the reaction temperature of the trimerization reaction
It it is 0~200 DEG C, reaction pressure is 0.5~20MPa, the reaction time is 0.1~5h.
14. method according to any one in Claims 1 to 4, it is characterised in that the reaction temperature of the trimerization reaction
It it is 50~150 DEG C, reaction pressure is 2~8MPa, the reaction time is 0.2~2h.
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| CN1993180A (en) * | 2004-06-18 | 2007-07-04 | Sasol技术股份有限公司 | Oligomerisation in the presence of both a tetramerisation catalyst and a further oligomerisation catalyst |
| CN101351424A (en) * | 2005-11-21 | 2009-01-21 | 国际壳牌研究有限公司 | Catalytic process for the oligomerization of olefinic monomers |
| CN102432415A (en) * | 2011-09-09 | 2012-05-02 | 中国科学院化学研究所 | Preparation method of ethylene-propylene copolymer |
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| CN1993180A (en) * | 2004-06-18 | 2007-07-04 | Sasol技术股份有限公司 | Oligomerisation in the presence of both a tetramerisation catalyst and a further oligomerisation catalyst |
| CN101351424A (en) * | 2005-11-21 | 2009-01-21 | 国际壳牌研究有限公司 | Catalytic process for the oligomerization of olefinic monomers |
| CN102432415A (en) * | 2011-09-09 | 2012-05-02 | 中国科学院化学研究所 | Preparation method of ethylene-propylene copolymer |
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