CN101816951A - Ethylene oligomerization catalyst and preparation method - Google Patents
Ethylene oligomerization catalyst and preparation method Download PDFInfo
- Publication number
- CN101816951A CN101816951A CN200910078393A CN200910078393A CN101816951A CN 101816951 A CN101816951 A CN 101816951A CN 200910078393 A CN200910078393 A CN 200910078393A CN 200910078393 A CN200910078393 A CN 200910078393A CN 101816951 A CN101816951 A CN 101816951A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sicl
- oligomerization
- obu
- mol ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an ethylene oligomerization catalyst, which comprises Zr(OBu)Cl3, SiClx-1R4-x(OBu), BuOH and SiClxR4-x in a mole ratio of 1:(0.5-5.0):(0-5.0):(0-20), wherein Bu is butyl; R is alkyl of C1 to C4 or aryl of C6 to C8; and x is an integer from 1 to 4. The catalyst has high reaction activity in an ethylene oligomerization reaction, a plurality of long chain hydrocarbons of C12 to C20 exist in an oligomerization product and the yield of alpha-olefin is high.
Description
Technical field
The present invention is a kind of ethylene oligomerisation catalyst and preparation method, specifically, is a kind of halogenated alkoxy Zr catalyst and preparation method thereof.
Background technology
Olefin oligomerization is an important component part of olefinic polyreaction, the expansion of specific products demand is caused the rise of oligomerisation reaction along with modern production life.Particularly the ethylene oligomerization reaction is used to prepare the alkene of higher carbochain.
Tradition and famous ethylene oligomerization technology is widely imitateed and learnt as Gulf, Ethyl, SHOP etc.Yet problem, particularly operating pressure such as there is the operating condition harshness in these traditional handicrafts, the one way catalyst activity is low, the product carbon number distribution is wide, product and raw material separation difficulty and waste liquid are difficult are too high, reach about 20MPa, have limited the economy of its technology.So, explore the technical research of under lower pressure, carrying out the ethylene oligomerization reaction more economic, easily row and never stop.
Comparatively speaking, bright dipping company be the catalyst system and catalyzing of major catalyst with the zirconium chloride because architecture is simple, reason such as operation is subjected to paying close attention to widely and studies in large quantities easily.USP4886933 uses two kinds of alkyl aluminum compounds to carry out preparing alpha-olefin by ethane oligomerisation as co-catalyst, USP4783573 adds the 3rd component on this basis and carries out ethylene oligomerization, the 3rd component is one or more Lewis alkali, as thiophene, methyl disulphide, thiocarbamide, triphenylphosphine or tri octyl phosphine, to reach the heat endurance that improves catalyst itself and to improve the purpose that product distributes, but still have a lot of deficiencies, too much as low-carbon alkene in the product, be apparent that C most
4Too much or active degradation down.
CN1021220C discloses a kind of catalyst of preparation of straight chain low carbon alpha olefine by use of vinyl oligomerization, and it is made up of zirconium compounds, organo-aluminum compound, alkali metal organic oxygen-containing compound and/or phosphine compound.Main employing zirconium chloride or zirconium alkoxide are the metal catalytic component, and organo-aluminum compound is alkyl aluminum or haloalkyl aluminium, comprises aluminium diethyl monochloride, dichloro one aluminium ethide and sesquialter ethylaluminium chloride etc., and the alkali metal organic oxygen-containing compound is phenol sodium or sodium alkoxide.Earlier all catalytic components that need add are mixed being warming up to 60～90 ℃ and carrying out ageing reaction 0.5～3.0 hour before the oligomerisation reaction, solvent is a chlorobenzene, carries out 1～2 hour oligomerisation reaction then at 70～100 ℃ of ethene that feed 1.4MPa.Among the embodiment that provides, the high catalytic activity of reaction is 3086g/gZrh, C in its product
10Following linear alpha-olefin content is 69%, C in the product
10Following linear alpha-olefin content is up to 87%, and this moment, catalyst activity was 879g/gZrh.
US20020147375A1 discloses the method that a kind of ethylene oligomerization prepares linear oligomer, major catalyst is a tetrabutyl zirconate, and co-catalyst is selected from sesquialter ethylaluminium chloride or triethyl aluminum, and best Al/Zr ratio is 1: 10～60, the butanols that contains small-amount free in the system, Zr (OR)
4With the ratio of free butanols be 1: 0.33～1.3, the oligomerisation reaction temperature is 80～140 ℃, pressure is 18～38kg/cm
2, solvent is cyclohexane or toluene.The highest reactivity is 4066g/gZrh in the example, used Zr (OBu)
40.33BuOH dosage is 0.125mmol, triethyl aluminum and sesquialter ethylaluminium chloride are respectively 1.56mmol and 4.7mmol, and the Al/Zr mol ratio is 50, and solvent is the reaction system of 200ml cyclohexane, at 125 ℃, 32kg/cm
2Condition under the reaction 3 hours, oligomerization product is distributed as: C
4: 41.7wt%, C
6～C
10: 51.3wt%, C
12～C
18: 6.9wt%, C
20 +: 0.1wt%.
Summary of the invention
The purpose of this invention is to provide a kind of ethylene oligomerisation catalyst and preparation method, this method for preparing catalyst is simple, is used for the catalyzed ethylene oligomerisation reaction, has advantages of high catalytic activity and reasonably product distribution.
Ethylene oligomerisation catalyst provided by the invention comprises the component with following mol ratio:
Zr(OBu)Cl
3∶(0.5～5.0)SiCl
x-1R
4-x(OBu)∶(0～5.0)BuOH∶(0～20)SiCl
xR
4-x
In the following formula, Bu is a butyl, and R is C
1～C
4Alkyl or C
6～C
8Aryl, x is 1～4 integer.
The present invention is an ethylene oligomerisation catalyst with the halogenated alkoxy zirconium of silicon modification, is used for the ethylene oligomerization reaction, has higher oligomerisation reaction activity, C in the oligomerization product
4And C
20 +Content few, alpha-olefin productive rate height.
The specific embodiment
The present invention generates butoxy tri-chlorination zirconium with excessive butanols reaction with zirconium chloride in aromatic hydrocarbon medium, unnecessary alcohol and general formula are SiCl
xR
4-xSilicon-containing compound reaction, generate and contain the silicon chloride compound of a butoxy, thereby effectively reduce the viscosity of catalyst system and catalyzing, increase activity of such catalysts and improve the distribution of oligomerization product, make C in the product
20 +Less relatively, C
6～C
20Component increases, and is convenient to the later separation purification operations, and linear alpha-olefin content also increases.
The key reaction of Preparation of Catalyst of the present invention is as follows:
Wherein, n is a positive integer.
BuOH+SiCl
xR
4-x→SiCl
x-1R
4-xOBu+HCl
Wherein, x is 1,2,3 or 4.
Contain Zr (OBu) Cl in the catalyst of the present invention
3And SiCl
X-1R
4-x(OBu) two kinds of solvents in addition, also may contain unreacted butanols and silicon-containing compound SiCl
xR
4-x
At silicon-containing compound SiCl
xR
4-xUnder the excessive situation, the component mol ratio that catalyst of the present invention has is:
Zr(OBu)Cl
3∶(2.0～5.0)SiCl
x-1R
4-x(OBu)∶(0.1～18)SiCl
xR
4-x。
The preferred ingredients mol ratio is:
Zr(OBu)Cl
3∶(2.0～5.0)SiCl
x-1R
4-x(OBu)∶(5～18)SiCl
xR
4-x。
Under the excessive situation of butanols, the component mol ratio that catalyst of the present invention has is:
Zr(OBu)Cl
3∶(0.5～4.0)SiCl
x-1R
4-x(OBu)∶(0.1～4.0)BuOH。
The preferred ingredients mol ratio is:
Zr(OBu)Cl
3∶(0.5～2.5)SiCl
x-1R
4-x(OBu)∶(0.5～2.5)BuOH。
Preparation of catalysts method provided by the invention, comprising suspends zirconium chloride stirs in the aromatic hydrocarbons, adds butanols and fully reacts, and being cooled to-5～5 ℃, to add general formulas be SiCl
xR
4-xSilicon-containing compound fully react SiCl
xR
4-xIn, R is C
1～C
4Alkyl or C
6～C
8Aryl, x is 1～4 integer.
The preferred n-butanol of the described butanols of said method.
The butanols that adds in the Preparation of Catalyst and the mol ratio of zirconium chloride are 3～9: 1, preferred 3～6: 1, and the temperature of zirconium chloride and butanols reaction is 60～120 ℃, preferred 70～100 ℃.
After zirconium chloride reacts with alcohol, the SiCl that adds when carrying out the silicon modification
xR
4-xWith the mol ratio of zirconium chloride be 0.1～18: 1, preferred 6～12: 1, SiCl
xR
4-xWith the reaction temperature of butanols be-5～5 ℃, preferred 0～5 ℃.
The preferred toluene of aromatic hydrocarbons that above-mentioned reaction is used.After reaction finishes, add an amount of aromatic hydrocarbons, be mixed with the modification chlorinated alkoxy zirconium oligomerization catalysis agent solution of required zirconium concentration.
The method of carrying out ethylene oligomerization with catalyst provided by the invention comprises: make ethene carry out oligomerisation reaction in the presence of catalyst for oligomerization of the present invention and aluminum alkyl catalyst.
Described aluminum alkyl catalyst is selected from aluminium diethyl monochloride, trichlorine triethyl group two aluminium, dichloro one aluminium ethide, triethyl aluminum or above-mentioned any two kinds mixture, the mixture of preferred trichlorine triethyl group two aluminium and triethyl aluminum.The mol ratio of zirconium is 5～20 in aluminium in the described aluminum alkyl catalyst and the catalyst for oligomerization, and is preferred 5～15, more preferably 5～10.
For improving the distribution of oligomerization product, when oligomerisation reaction, add second kind of auxiliary agent, described second kind of auxiliary agent is selected from piperidine oxide, and be preferred 2,2,6,6-tetramethyl piperidine-nitrogen-oxide.The mol ratio of the middle zirconium of second kind of auxiliary agent and catalyst for oligomerization is 0.05～1.0.
Described oligomerisation reaction temperature is 20～120 ℃, preferred 50～100 ℃, and pressure is 1～6MPa, preferred 2～4MPa, and the reaction time is 0.5～5.0 hour, preferred 0.5～2.0 hour.
Further describe the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare catalyst for oligomerization of the present invention.
The 10mmol zirconium chloride is suspended in the toluene of 26g, 70 ℃ were stirred 1 hour, add the 30mmol n-butanol, 85 ℃ of back flow reaction 4 hours are cooled to 0 ℃, add the silicon tetrachloride reaction 4.0 hours of 80mmol, the toluene that adds 7.0g, obtaining zirconium concentration is the catalyst for oligomerization solution A of 0.2 mol, and by the HCl that generates is carried out quantitative analysis, the mol ratio that records each component wherein is as follows:
Zr(On-Bu)Cl
3∶2.0SiCl
3(On-Bu)∶6.0SiCl
4
Example 2
Prepare catalyst for oligomerization of the present invention.
The zirconium chloride of 2.33g (10mmol) is suspended in the toluene of 34.6g, 70 ℃ were stirred 1 hour, add the 40mmol n-butanol, 100 ℃ of back flow reaction 4 hours are cooled to 0 ℃, add the silicon tetrachloride reaction 3.0 hours of 0.8mmol, the toluene that adds 5.45g, obtaining zirconium concentration is the catalyst for oligomerization solution B of 0.2 mol, and by the HCl that generates is carried out quantitative analysis, the mol ratio that records each component wherein is as follows:
Zr(On-Bu)Cl
3∶0.8SiCl
3(On-Bu)∶2.2(n-BuOH)
Example 3
Prepare catalyst for oligomerization of the present invention.
The 10mmol zirconium chloride is suspended in the toluene of 34.6g, 70 ℃ were stirred 1 hour, add the 50mmol n-butanol, 90 ℃ of back flow reaction 4 hours are cooled to 0 ℃, add the silicon tetrachloride reaction 4.0 hours of 30mmol, the toluene that adds 1.77g, obtaining zirconium concentration is the catalyst for oligomerization solution C of 0.2 mol, and by the HCl that generates is carried out quantitative analysis, the mol ratio that records each component wherein is as follows:
Zr(On-Bu)Cl
3∶3.0SiCl
3(On-Bu)∶1.0(n-BuOH)
Example 4
Prepare catalyst for oligomerization of the present invention.
The 10mmol zirconium chloride is suspended in the toluene of 26g, 70 ℃ were stirred 1 hour, add the 30mmol n-butanol, 85 ℃ of back flow reaction 4 hours are cooled to 0 ℃, add the silicon tetrachloride reaction 3.5 hours of 100mmol, the toluene that adds 5.0g, obtaining zirconium concentration is the catalyst for oligomerization solution D of 0.2 mol, and by the HCl that generates is carried out quantitative analysis, the mol ratio that records each component wherein is as follows:
Zr(On-Bu)Cl
3∶2.0SiCl
3(On-Bu)∶8.0SiCl
4
Example 5
Prepare catalyst for oligomerization of the present invention.
The 10mmol zirconium chloride is suspended in the toluene of 17.3g, 70 ℃ were stirred 1 hour, add the 30mmol n-butanol, 85 ℃ of back flow reaction 4 hours are cooled to 0 ℃, add the silicon tetrachloride reaction 3.5 hours of 167mmol, the toluene that adds 7.05g, obtaining zirconium concentration is the catalyst for oligomerization solution E of 0.2 mol, and by the HCl that generates is carried out quantitative analysis, the mol ratio that records each component wherein is as follows:
Zr(On-Bu)Cl
3∶2.0SiCl
3(On-Bu)∶14.7SiCl
4
Example 6
Prepare catalyst for oligomerization of the present invention.
The 10mmol zirconium chloride is suspended in the toluene of 26g, 70 ℃ were stirred 1 hour, add the 30mmol n-butanol, 85 ℃ of back flow reaction 4 hours are cooled to 0 ℃, add the trim,ethylchlorosilane reaction 4.0 hours of 80mmol, the toluene that adds 6.11g, obtaining zirconium concentration is the oligomerization catalysis agent solution F of 0.2 mol, and by the HCl that generates is carried out quantitative analysis, the mol ratio that records each component wherein is as follows:
Zr(On-Bu)Cl
3∶2.0Si(CH
3)
3(On-Bu)∶6.0Si(CH
3)
3Cl
Example 7
Prepare catalyst for oligomerization of the present invention.
The 10mmol zirconium chloride is suspended in the toluene of 26g, 70 ℃ were stirred 1 hour, add the 30mmol n-butanol, 85 ℃ of back flow reaction 4 hours are cooled to 0 ℃, add the diphenyl dichlorosilane reaction 4.0 hours of 80mmol, the toluene that adds 0.55g, obtaining zirconium concentration is the oligomerization catalysis agent solution G of 0.2 mol, and by the HCl that generates is carried out quantitative analysis, the mol ratio that records each component wherein is as follows:
Zr(On-Bu)Cl
3∶2.0SiCl(Ph)
2(On-Bu)∶6.0Si(Ph)
2Cl
2
Example 8
Following example carries out the ethylene oligomerization reaction.
Under the anhydrous and oxygen-free condition, trichlorine triethyl group two aluminium, the 1.15ml concentration that add 200ml toluene, 1.75ml concentration successively and be 2.0 mol in reactor are the triethyl aluminum of 1.0 mol, 2.6ml the catalyst for oligomerization B solution of example 2 preparations, making by the Al/Zr mol ratio is 9.Charge into ethene to 3.0MPa in reactor, 80 ℃ were reacted 1 hour.Reaction is cooled to 25 ℃ after finishing, and gets rid of gas products, collects product liquid, and adding a little concentration is the NaOH ethanolic solution cessation reaction of 0.5 mol, through washing, drying, obtains oligomerization product.Catalyst activity is 4.69 * 10
5GOligomermolZr
-1H
-1Oligomerization product distributes and sees Table 1, the oligomerization product gas Chromatographic Determination.
Example 9
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization C of example 3 preparations, and the catalyst for oligomerization activity is 4.31 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 10
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization D of example 4 preparations, and the catalyst for oligomerization activity is 6.40 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 11
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization E of example 5 preparations, and the catalyst for oligomerization activity is 3.63 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 12
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization F of example 6 preparations, and the catalyst for oligomerization activity is 1.05 * 10
6GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 13
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization G of example 7 preparations, and the catalyst for oligomerization activity is 1.34 * 10
6GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 14
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization A of example 1 preparation, and the catalyst for oligomerization activity is 6.49 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 15
Under the anhydrous and oxygen-free condition, in reactor, add 200ml toluene successively, 2.35ml concentration is trichlorine triethyl group two aluminium of 2.0 mol, the catalyst for oligomerization A solution of 2.6ml example 1 preparation, making the Al/Zr mol ratio is 9.Charge into ethene to 3.0MPa in reactor, 80 ℃ were reacted 1 hour.Reaction is cooled to 25 ℃ after finishing, and gets rid of gas products, collects product liquid, and adding a little concentration is the NaOH ethanolic solution cessation reaction of 0.5 mol, through washing, drying, obtains oligomerization product.Catalyst activity is 2.09 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 16
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization A of example 1 preparation, and trichlorine triethyl group two aluminium of adding are 3.5ml, and triethyl aluminum is 2.3ml, making the Al/Zr mol ratio is 18, and the catalyst for oligomerization activity is 8.29 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 17
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization A of example 1 preparation, and in 100 ℃ of reactions 1 hour, catalyst activity was 3.98 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 18
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization A of example 1 preparation, and reaction pressure is 4.0MPa, and catalyst activity is 6.79 * 10
6GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Example 19
Under the anhydrous and oxygen-free condition, in reactor, add 200ml toluene successively, 5.4ml concentration is trichlorine triethyl group two aluminium of 2.0 mol, 3.5ml concentration is the triethyl aluminum of 1.0 mol, 2.6ml the catalyst for oligomerization A solution of example 1 preparation, making the Al/Zr mol ratio is 9, the TEMPO (2 of 0.156g, 2,6,6-tetramethyl piperidine-nitrogen-oxide), making the N/Zr mol ratio is 0.1.Charge into ethene to 3MPa in reactor, 80 ℃ were reacted 1 hour.Reaction is cooled to 25 ℃ after finishing, and gets rid of gas products, collects product liquid, and adds the NaOH ethanolic solution cessation reaction that a little concentration is 0.5 mol, through washing, drying, obtains oligomerization product.Catalyst activity is 3.98 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Comparative example 1
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is 0.5mmolZrCl
4, after oligomerisation reaction finished, the catalyst activity that records was 3.72 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Comparative example 2
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is 0.5mmolZrCl
4, and reaction temperature is 100 ℃, after oligomerisation reaction finished, the catalyst activity that records was 2.81 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Comparative Examples 3
Carry out the ethylene oligomerization reaction by the method for example 8, the different catalyst that is to use is the catalyst for oligomerization A of example 1 preparation, and trichlorine triethyl group two aluminium of adding are 5.4ml, and triethyl aluminum is 3.5ml, making the Al/Zr mol ratio is 30, and the catalyst for oligomerization activity is 1.32 * 10
6GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Comparative Examples 4
Under the anhydrous and oxygen-free condition, in reactor, add 200ml toluene successively, 5.4ml concentration is trichlorine triethyl group two aluminium of 2.0 mol, 3.5ml concentration is the triethyl aluminum of 1.0 mol, 2.6ml the catalyst for oligomerization A solution of example 1 preparation, making the Al/Zr mol ratio is 30, the TEMPO (2 of 0.156g, 2,6,6-tetramethyl piperidine-nitrogen-oxide), making the N/Zr mol ratio is 0.2.Charge into ethene to 3MPa in reactor, 80 ℃ were reacted 1 hour.Reaction is cooled to 25 ℃ after finishing, and gets rid of gas products, collects product liquid, and adds the NaOH ethanolic solution cessation reaction that a little concentration is 0.5 mol, through washing, drying, obtains oligomerization product.Catalyst activity is 3.43 * 10
5GOligomermolZr
-1H
-1, oligomerization product distributes and sees Table 1.
Table 1
Claims (15)
1. ethylene oligomerisation catalyst comprises the component with following mol ratio:
Zr(OBu)Cl
3∶(0.5～5.0)SiCl
x-1R
4-x(OBu)∶(0～5.0)BuOH∶(0～20)SiCl
xR
4-x
In the following formula, Bu is a butyl, and R is C
1～C
4Alkyl or C
6～C
8Aryl, x is 1～4 integer.
2. according to the described catalyst of claim 1, it is characterized in that the component mol ratio that described catalyst has is:
Zr(OBu)Cl
3∶(2.0～5.0)SiCl
x-1R
4-x(OBu)∶(0.1～18)SiCl
xR
4-x。
3. according to the described catalyst of claim 2, it is characterized in that the component mol ratio that described catalyst has is:
Zr(OBu)Cl
3∶(2.0～5.0)SiCl
x-1R
4-x(OBu)∶(5～18)SiCl
xR
4-x。
4. according to the described catalyst of claim 1, it is characterized in that the component mol ratio that described catalyst has is:
Zr(OBu)Cl
3∶(0.5～4.0)SiCl
x-1R
4-x(OBu)∶(0.1～4.0)BuOH。
5. according to the described catalyst of claim 4, it is characterized in that the component mol ratio that described catalyst has is:
Zr(OBu)Cl
3∶(0.5～2.5)SiCl
x-1R
4-x(OBu)∶(0.5～2.5)BuOH。
6. described Preparation of catalysts method of claim 1, comprising suspends zirconium chloride stirs in the aromatic hydrocarbons, adds butanols and fully reacts, and being cooled to 0～5 ℃, to add general formula be SiCl
xR
4-xSilicon-containing compound fully react SiCl
xR
4-xIn, R is C
1～C
4Alkyl or C
6～C
8Aryl, x is 1～4 integer.
7. according to the described catalyst of claim 6, it is characterized in that described butanols is a n-butanol.
8. according to the described catalyst of claim 6, it is characterized in that the butanols that adds and the mol ratio of zirconium chloride are 3～9: 1, the temperature of zirconium chloride and butanols reaction is 60～120 ℃.
9. according to the described catalyst of claim 6, it is characterized in that the SiCl that adds
xR
4-xWith the mol ratio of zirconium chloride be 0.5～18, SiCl
xR
4-xWith the reaction temperature of butanols be-5～5 ℃.
10. according to the described catalyst of claim 6, it is characterized in that described aromatic hydrocarbons is toluene.
11. an ethylene oligomerization method comprises making ethene carry out oligomerisation reaction in the presence of described catalyst for oligomerization of claim 1 and aluminum alkyl catalyst.
12. in accordance with the method for claim 11, it is characterized in that described aluminum alkyl catalyst is selected from aluminium diethyl monochloride, trichlorine triethyl group two aluminium, dichloro one aluminium ethide or triethyl aluminum.
13. it is characterized in that in accordance with the method for claim 11, the mol ratio of zirconium in aluminium in the described aluminum alkyl catalyst and the catalyst for oligomerization is 5～20.
14. in accordance with the method for claim 11, it is characterized in that adding second kind of auxiliary agent when oligomerisation reaction, described second kind of auxiliary agent is selected from piperidine oxide.
15. it is characterized in that in accordance with the method for claim 14, the mol ratio of the middle zirconium of described second kind of auxiliary agent and catalyst for oligomerization is 0.05～1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100783937A CN101816951B (en) | 2009-02-27 | 2009-02-27 | Ethylene oligomerization catalyst and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100783937A CN101816951B (en) | 2009-02-27 | 2009-02-27 | Ethylene oligomerization catalyst and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101816951A true CN101816951A (en) | 2010-09-01 |
| CN101816951B CN101816951B (en) | 2013-01-09 |
Family
ID=42652313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100783937A Active CN101816951B (en) | 2009-02-27 | 2009-02-27 | Ethylene oligomerization catalyst and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101816951B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206447A (en) * | 2017-07-06 | 2019-01-15 | 中国石油化工股份有限公司 | Ethylene oligomerisation catalyst and its preparation method and application |
| CN109201119A (en) * | 2017-07-06 | 2019-01-15 | 中国石油化工股份有限公司 | Catalyst system for ethylene oligomerization and its preparation method and application |
| CN109206292A (en) * | 2017-07-06 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of method of ethylene oligomerization for prepn. of alpha-olefines |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4041226A (en) * | 1974-12-12 | 1977-08-09 | Anderson Development Company | Chromium tris-diorgano-orthophosphate-alkyl aluminum halide catalysts for olefin polymerization and alkylation of aromatic compounds |
| US5155079A (en) * | 1991-06-07 | 1992-10-13 | Quantum Chemical Corporation | Multiple site olefin polymerization catalysts |
| CN1160700A (en) * | 1996-03-21 | 1997-10-01 | 抚顺石油化工公司研究院 | Continuous ethylene oligomerization process preparing straight-chain low-carbon alpha-alkene |
-
2009
- 2009-02-27 CN CN2009100783937A patent/CN101816951B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206447A (en) * | 2017-07-06 | 2019-01-15 | 中国石油化工股份有限公司 | Ethylene oligomerisation catalyst and its preparation method and application |
| CN109201119A (en) * | 2017-07-06 | 2019-01-15 | 中国石油化工股份有限公司 | Catalyst system for ethylene oligomerization and its preparation method and application |
| CN109206292A (en) * | 2017-07-06 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of method of ethylene oligomerization for prepn. of alpha-olefines |
| CN109206292B (en) * | 2017-07-06 | 2021-06-11 | 中国石油化工股份有限公司 | Method for preparing alpha-olefin by ethylene oligomerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101816951B (en) | 2013-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8481444B2 (en) | Catalyst composition for oligomerization of ethylene oligomerization process and method for its preparation | |
| CA2878634C (en) | Method for oligomerization of ethylene | |
| US20210355049A1 (en) | Antifouling oligomerization catalyst systems | |
| CN1184240C (en) | Olefin production | |
| CA2711093C (en) | Method for preparing linear alpha-olefins | |
| TWI615380B (en) | Catalyst composition and process for oligomerization of ethylene to produce 1-hexene and/or 1-octene | |
| EA039177B1 (en) | Method of oligomerization of olefins | |
| JP7212027B2 (en) | Method for preparing ethylene oligomerization catalyst and method for oligomerization thereof | |
| EP0722922B1 (en) | Manufacture of linear alpha-olefins | |
| CN108602909A (en) | The manufacturing method and catalyst of oligomer | |
| CN104245712B (en) | Ethylene oligomerisation processes | |
| CN1079786C (en) | Process for preparation of alpha-olefins | |
| TW200930456A (en) | Catalyst composition and process for preparing linear alpha-olefins | |
| CN101816951B (en) | Ethylene oligomerization catalyst and preparation method | |
| CN101745422B (en) | Olefin oligomerization catalyst and preparation method and application thereof | |
| CN113260457B (en) | Ligand for producing 1-hexene in chromium-assisted ethylene oligomerization process | |
| CN107250170A (en) | The manufacture method of olefin polymerization catalysis and olefin oligomer | |
| CN110753695B (en) | Heteroatom ligand, oligomerization catalyst containing same and preparation method of oligomer | |
| CN103100419B (en) | Mixed decene oligomerization catalyst | |
| CN113242764B (en) | Ligand for producing 1-octene in chromium-assisted ethylene oligomerization process | |
| US11325874B2 (en) | Method for preparing a linear alpha olefin including oxygen removal from the feed | |
| CN109201119B (en) | Ethylene oligomerization catalyst system, preparation method and application thereof | |
| EP3736257A1 (en) | Method for preparing paraffin | |
| CN106927988B (en) | Preparation method of decene | |
| RU2423371C2 (en) | Method of producing 1-ethyl-2,3-dialkyl(phenyl)aluminacyclopent-2-enes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |