CN107282119B - Catalyst composition for ethylene oligomerization and oligomerization method - Google Patents
Catalyst composition for ethylene oligomerization and oligomerization method Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- 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
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- 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
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Abstract
The invention discloses a catalyst composition for an ethylene oligomerization reaction process and application thereof, wherein the composition comprises a main catalyst chlorinated substituted-2-formyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for an ethylene oligomerization reaction process.
Background
The linear alpha-olefin has wide application in the fields of ethylene comonomer, surfactant synthetic intermediate, alcohol for plasticizer, synthetic lubricating oil, oil additive and the like. In recent years, with the continuous development of the polyolefin industry, the worldwide demand for α -olefins has rapidly increased. At present, most of alpha-olefin is prepared by ethylene oligomerization. The catalysts used in the ethylene oligomerization method mainly comprise nickel-based, chromium-based, zirconium-based and aluminum-based catalysts, and in recent years, Brookhart group (Brookhart, M et al, J.Am.chem.Soc.,1998,120, 7143-containing 7144; WO99/02472,1999), Gibson group (Gibson, V.C.et al, chem.Commun.,1998, 849-containing 850; chem.Eur.J.,2000, 2221-containing 2231) respectively find that the tridentate pyridine imine complexes of Fe (II) and Co (II) can catalyze the ethylene oligomerization, and not only the catalytic activity of the catalyst is high, but also the selectivity of alpha-olefin is high.
At present, water and oxygen are generally considered to be very unfavorable for the ethylene oligomerization reaction process, and CN200810111717.8 discloses a method for ethylene oligomerization, which is strictly controlled to be performed in an anhydrous and oxygen-free environment, so that the current ethylene oligomerization reaction has very strict process requirements, resulting in very poor reaction initiation and repeatability of the oligomerization reaction process.
Disclosure of Invention
Aiming at the defects in the prior art, the inventor carries out extensive and intensive research in the field of catalysts for ethylene oligomerization, and surprisingly discovers that ethylene is oligomerized under the action of a catalyst composition comprising a main catalyst chlorinated substituted-2-formyl-1, 10-phenanthroline condensed-2, 6-diethylaniline iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solvent, and the catalyst composition has higher oligomerization activity, and the oligomerization is quick in initiation, stable in operation and good in repeatability; thereby overcoming the technical bias of the technicians in the field and achieving unexpected technical effects.
According to one aspect of the present invention, there is provided a catalyst composition for ethylene oligomerization, the composition comprising a main catalyst chlorinated substituted-2-formyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex represented by formula (I):
in the formula (I), R1-R6Each independently selected from hydrogen and C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
The catalyst composition provided by the invention has high ethylene oligomerization reaction activity and high alpha-olefin selectivity.
In the present invention, said R1-R6The choice of (a) may be any combination of the substituents referred to by the above terms. Wherein, in a preferred embodiment of the present invention, R in the main catalyst1-R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitro; wherein R is1-R6The choice of (a) may be any combination of the above groups. In one embodiment of the above composition, R in the procatalyst3And R4Is methyl, R1、R2、R5And R6Are all hydrogen.
In a preferred embodiment of the present invention, the aluminum-containing cocatalyst is selected from at least one of aluminoxanes and alkylaluminum compounds. In the present invention, the alkyl aluminum compound has the general formula AlRnXmWherein each R is independently a straight or branched chain C1-C8An alkyl group; each X is halogen, preferably chlorine or bromine; n is an integer of 1 to 3, m is an integer of 0 to 2, and m + n is equal to 3. Specific examples of the alkyl aluminum compound include, but are not limited to, at least one of the following compounds: trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride, such as triethylaluminum. In the present invention, the aluminoxane is C1-C4Alkylaluminoxane of which C1-C4The alkyl group is a linear or branched alkyl group. Examples of the aluminoxane include, but are not limited to: at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; such as methylaluminoxane.
In a preferred embodiment of the invention, the molar ratio of aluminium in the cocatalyst to iron in the procatalyst is from 30:1 to 900:1, such as from 100:1 to 700:1, further such as from 148:1 to 196: 1. In a specific embodiment of the above composition, the molar ratio of aluminum in the co-catalyst to iron in the main catalyst is from 196:1 to 500: 1. The ethylene oligomerization activity in the composition is still high even in the lower molar ratio ranges provided.
In a preferred embodiment of the present invention, the catalyst composition comprises 5 to 1750ppm, such as 25 to 1750ppm, by weight of t-butyl hydroperoxide. In a specific example, the weight content of the tert-butyl hydroperoxide is 35-1300 ppm, such as 100-1300 ppm. Under the preferable condition, the weight content of the tert-butyl hydroperoxide is 250-1000 ppm. Within the content range of the tert-butyl hydroperoxide, the catalyst composition has higher ethylene oligomerization activity.
In a preferred embodiment of the present invention, the composition further comprises an organic solvent, that is, the composition comprises a main catalyst chlorinated substituted-2-formyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex shown in formula (I), an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solvent. In the present invention, the weight content of the t-butyl hydroperoxide is calculated based on the weight of the organic solvent. For example, the content of t-butyl hydroperoxide is 5 to 1750ppm by weight based on the weight of the organic solvent, i.e., 5 to 1750X 10 based on 1g of the organic solvent-6g of tert-butyl hydroperoxide. The organic solvent is an organic solvent commonly used in the art, and specific examples thereof include, but are not limited to: at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and methylene chloride, such as toluene, xylene, or a mixture of toluene and xylene.
In the case of using the composition of the present invention in production, the amounts of the main catalyst and the cocatalyst can be selected according to the production scale and the process conditions of the specific application such as production equipment. In one embodiment of the catalyst compositionThe content of the main catalyst is 2 to 500 [ mu ] mol/L (i.e., 2 to 500X 10 in the composition based on 1L of the composition) based on the volume of the composition containing the organic solvent-6mol of main catalyst), such as 20-100 μmol/L, such as 50 μmol/L.
According to another aspect of the invention, a method for oligomerization of ethylene is also provided. The catalyst composition can be applied to oligomerization of ethylene, and ethylene oligomerization reaction is carried out on the ethylene under the catalysis of the catalyst composition. One specific embodiment may include the steps of: (1) replacing the reaction system through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction system is anhydrous and anaerobic; (2) replacing the reaction system by using ethylene to ensure that the reaction system is in an ethylene environment; (3) adding a catalyst composition comprising a main catalyst, a cocatalyst and tert-butyl hydroperoxide (and an organic solvent) into a reaction system, and fully stirring; (4) the oligomerization reaction is carried out by starting the oligomerization reaction with ethylene, and may be carried out, for example, under the following conditions: maintaining the reaction pressure at 0.1 to 30MPa, the reaction temperature at-20 to 150 ℃, and the reaction time at 30 to 100 min; (5) the reaction was stopped after a certain time. The reaction product was analyzed by Gas Chromatography (GC).
In the invention, the main catalyst and the cocatalyst in the step (3) can be dissolved by an organic solvent and then added into the reaction system. In the oligomerization reaction process, the main catalyst and the cocatalyst are mixed in an ethylene atmosphere. The temperature of the oligomerization reaction is-20 to 150 ℃, for example, 0 to 80 ℃. Under preferred conditions, the temperature ranges from-20 to 40 deg.C, such as 5 to 35 deg.C. The reaction pressure is 0.1-30 MPa, and the oligomerization activity is increased along with the increase of the ethylene pressure.
The catalyst composition is used for ethylene oligomerization, and the obtained ethylene oligomerization product comprises C4、C6、C8、C10、C12、C14、C16、C18、C20、C22Etc.; the selectivity of alpha-olefin can reach about 96 percent. After the ethylene oligomerization reaction was completed, GC analysis was performed. The result shows that oligomerizationActivity can reach 107g·mol(Fe)-1·h-1The above. In addition, the remaining reaction mixture was neutralized with a 5% diluted hydrochloric acid acidified ethanol solution, and no polymer was obtained.
According to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of a main catalyst chlorinated substituted-2-formyl-1, 10-phenanthroline iron (II) complex shown in formula (I), an aluminum-containing cocatalyst, tert-butyl hydrogen peroxide and an organic solvent, so that the catalyst composition has high oligomerization reaction activity, high alpha-olefin selectivity, quick oligomerization reaction initiation, stable operation and good repeatability. According to the invention, the oligomerization reaction activity is better even under the condition of very low Al/Fe ratio. According to the invention, the oligomerization activity is still high when the reaction is carried out at a relatively low temperature. According to the invention, the technical bias of technicians in the field is overcome, and unexpected technical effects are achieved; the catalytic effect and the cost are well balanced, so that the ethylene oligomerization reaction cost is greatly reduced, the practicability is high, and the industrialization prospect is wide.
Detailed Description
The invention is further illustrated and described with reference to specific examples, which are not intended to be limiting.
Example 1
The ethylene oligomerization reaction specifically comprises the following steps: (1) replacing the reaction system through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction system is anhydrous and anaerobic; (2) replacing the reaction system by using ethylene to ensure that the reaction system is in an ethylene environment; (3) adding tert-butyl hydroperoxide and toluene solvent into a reaction kettle, adding 1.37ml of triethyl aluminum toluene solution (the concentration is 715 mu mol/ml), adding 2ml of chloro-2-formyl-5, 6-dimethyl-1, 10-phenanthroline condensation-2, 6-diethyl aniline iron (II) complex (R)3And R4Is methyl, R1、R2、R5And R6All hydrogen) was added to the reaction solution, and the total amount of the composition was adjusted to 100mL (concentration: 2.5. mu. mol/mL), wherein the weight of the organic solvent (toluene) was used as a reference, and the amount of tert-butyl group was adjusted to 100mLHydrogen peroxide weight content is 25ppm, Al/Fe is 196, after fully stirring, ethylene is introduced to start oligomerization reaction; (4) keeping the ethylene pressure at 1MPa and the reaction temperature at 30 ℃ for reacting for 30 minutes; (7) the reaction was stopped and a small amount of the reaction product was taken out for analysis by Gas Chromatography (GC): the oligomerization activity is 0.94X 107g·mol(Fe)-1·h-1The oligomer content is respectively C4 48.48％，C6～C1047.81％，C6～C1852.90% (containing linear alpha-olefins 95.5%), C20～C280.77 percent. The remaining mixture was neutralized with 5% hydrochloric acid acidified ethanol solution, no polymer was obtained. The analysis results are shown in table one.
Example 2
The same as in example 1, except that the content of t-butyl hydroperoxide was 100ppm by weight. The data are shown in Table 1.
Example 3
The same as in example 1, except that the content of t-butyl hydroperoxide was 250ppm by weight. The data are shown in Table 1.
Example 4
The same as in example 1, except that the content of t-butyl hydroperoxide was 500ppm by weight. The data are shown in Table 1.
Example 5
The same as in example 1, except that the content by weight of t-butyl hydroperoxide was 1000 ppm. The data are shown in Table 1.
Example 6
The difference from example 1 is that the t-butyl hydroperoxide content was 1300ppm by weight. The data are shown in Table 1.
Example 7
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 1750ppm by weight, the data being shown in Table 1.
Example 8
The same as in example 1, except that the t-butyl hydroperoxide was contained in an amount of 500ppm by weight and the reaction temperature was 0 ℃. The data are shown in Table 1.
Example 9
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and the reaction temperature is-10 ℃. The data are shown in Table 1.
Example 10
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and the reaction temperature is-20 ℃. The data are shown in Table 1.
Example 11
The same as in example 1, except that the t-butyl hydroperoxide content was 500ppm by weight and the reaction temperature was 40 ℃. The data are shown in Table 1.
Example 12
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and that Al/Fe is 500. The data are shown in Table 1.
Comparative example 1
The same as example 1, except that t-butyl hydroperoxide was not present in the composition. The data are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, according to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of a composition comprising a main catalyst chlorinated substituted 2-formyl-1, 10-phenanthroline-2, 6-diethylaniline iron (II) complex shown in formula (I), an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solvent, and the catalyst composition has high oligomerization reaction activity, high alpha-olefin selectivity, quick initiation of oligomerization reaction, stable operation and good repeatability. According to the invention, the oligomerization reaction activity is better even under the condition of very low Al/Fe ratio. According to the invention, the oligomerization activity is still high when the reaction is carried out at a relatively low temperature.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (16)
1. A catalyst composition for ethylene oligomerization comprises a main catalyst chlorinated substituted 2-formyl-1, 10-phenanthroline iron (II) complex shown as a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide:
in the formula, R1～R6Each independently selected from hydrogen and C1～C6Alkyl, halogen, C1～C6The composition further comprises an organic solvent, the weight content of tert-butyl hydroperoxide is 5-1750 ppm by taking the weight of the organic solvent as a reference, the molar ratio of aluminum in the cocatalyst to iron in the main catalyst is 30: 1-900: 1, and the aluminum-containing cocatalyst is selected from at least one of aluminoxane and an alkyl aluminum compound.
2. The catalyst composition of claim 1, wherein the weight content of t-butyl hydroperoxide in the catalyst composition is 35 to 1300ppm, based on the weight of the organic solvent.
3. The catalyst composition of claim 1, wherein the t-butyl hydroperoxide is present in an amount of 250 to 1000ppm by weight.
4. The catalyst composition of any of claims 1-3, wherein the molar ratio of aluminum in the co-catalyst to iron in the main catalyst is from 100:1 to 700: 1.
5. The catalyst composition of claim 4, wherein the molar ratio of aluminum in the co-catalyst to iron in the main catalyst is from 196:1 to 500: 1.
6. The catalyst composition of any of claims 1-3, wherein R in the procatalyst is1-R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitro.
7. The catalyst composition of claim 6, wherein R in the procatalyst is3And R4Is methyl, R1、R2、R5And R6Are all hydrogen.
8. The catalyst composition according to claim 1, characterized in that the alkylaluminum compound has the general formula AlRnXmWherein each R is independently a straight or branched chain C1-C8An alkyl group; x is halogen; n is an integer of 1 to 3, m is an integer of 0 to 2, and m + n is equal to 3.
9. The catalyst composition of claim 8, wherein the halogen is chlorine or bromine.
10. The catalyst composition of claim 8, wherein the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, and ethylaluminum dichloride.
11. The catalyst composition of claim 1, wherein the aluminoxane is C1-C4Alkylaluminoxane of which C1-C4The alkyl group is a linear or branched alkyl group.
12. The catalyst composition of claim 11, wherein the aluminoxane is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
13. The catalyst composition according to any one of claims 1 to 3, characterized in that the organic solvent is selected from at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene and dichloromethane.
14. The catalyst composition of claim 13, wherein the amount of the main catalyst in the catalyst composition is 2 to 500 μmol/L, based on the volume of the composition.
15. The catalyst composition of claim 14, wherein the amount of the main catalyst in the catalyst composition is 20 to 100 μmol/L, based on the volume of the composition.
16. A process for oligomerization of ethylene, wherein ethylene is subjected to the oligomerization of ethylene under the catalysis of the catalyst composition of any one of claims 1 to 15.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009080237A1 (en) * | 2007-12-21 | 2009-07-02 | Basell Polyolefine Gmbh | Catalyst sytem for olefin polymerization comprising phenantroline-comprising iron complexes |
| CN104415789A (en) * | 2013-08-26 | 2015-03-18 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization and ethylene oligomerization method |
| CN104974281A (en) * | 2014-04-11 | 2015-10-14 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction, catalyst and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009080237A1 (en) * | 2007-12-21 | 2009-07-02 | Basell Polyolefine Gmbh | Catalyst sytem for olefin polymerization comprising phenantroline-comprising iron complexes |
| CN104415789A (en) * | 2013-08-26 | 2015-03-18 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization and ethylene oligomerization method |
| CN104974281A (en) * | 2014-04-11 | 2015-10-14 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction, catalyst and preparation method thereof |
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