CN117563674A - Ethylene oligomerization catalyst and application thereof - Google Patents

Ethylene oligomerization catalyst and application thereof Download PDF

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CN117563674A
CN117563674A CN202311306822.8A CN202311306822A CN117563674A CN 117563674 A CN117563674 A CN 117563674A CN 202311306822 A CN202311306822 A CN 202311306822A CN 117563674 A CN117563674 A CN 117563674A
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catalyst
chromium
reaction
formula
ethylene
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吕英东
刘建峰
李小冬
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides an ethylene oligomerization catalyst and application thereof, comprising a binuclear chromium catalyst and a cocatalyst, wherein the binuclear chromium catalyst has the following structure:n is 1 to 3. The binuclear chromium catalyst of the invention is used for carrying out the selective tetramerization reaction of ethylene, can generate 1-octene with high selectivity, and has high catalytic activity and high production efficiency.

Description

Ethylene oligomerization catalyst and application thereof
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to an ethylene oligomerization catalyst and application thereof.
Background
1-octene is mainly used for producing high-end PE and POE, and is used as a raw material for producing plasticizers, alcohols for detergents and lubricating oil additives, and is an important organic raw material and a chemical intermediate. At present, ethylene selective oligomerization is one of the main methods for industrially preparing linear 1-octene.
Patent CN100548946C discloses a catalytic system of PNP ligand, chromium source and methylaluminoxane, by which ethylene selective tetramerization can be realized, and industrial production of 1-octene is realized. But the selectivity of 1-octene in the product is only 70%, and generally, the product also contains about 20% of by-product hexene and 10% of other various olefins, so that the raw material utilization rate is low and the production cost is high.
How to further improve the selectivity of the 1-octene and reduce the production cost of the 1-octene is the focus of research in the field.
Disclosure of Invention
The invention aims to provide an ethylene oligomerization catalyst, which is used for efficiently enabling ethylene to carry out tetramerization reaction with high selectivity by adopting a binuclear chromium catalyst system to prepare 1-octene, and has high catalyst activity and good catalytic effect.
The invention also provides application of the catalyst in the field of ethylene oligomerization.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an ethylene oligomerization catalyst comprises a binuclear chromium catalyst and a cocatalyst, wherein the binuclear chromium catalyst has the following structure:
n is 1-3;
preferably, the binuclear chromium catalyst is prepared by reacting a biphosphine ligand with a chromium source.
Preferably, the structure of the biphosphine ligand is as follows:n is 1 to 3.
Preferably, the chromium source is tetrahydrofuran chromium chloride or chromium chloride.
Preferably, the reaction is carried out in a solvent selected from tetrahydrofuran, methyltetrahydrofuran.
The reaction scheme is shown below:
preferably, the molar ratio of the diphosphine ligand to chromium in the chromium source is 1:1 to 1:1.1;
preferably, the reaction temperature is 0-50 ℃, and the reaction pressure is normal pressure.
Preferably, the selected biphosphine ligand is prepared by reacting a difuranyl phosphine chloride represented by formula I with a dibromoalkane represented by formula II under the action of alkyl lithium.
Wherein n is 1-3;
the reaction scheme is shown below:
preferably, the molar ratio of dibromoalkane shown in the formula II to difuranyl phosphine chloride shown in the formula I is 0.5-0.6:1.
Preferably, the molar ratio of the alkyl lithium to the difuranyl phosphine chloride shown in the formula I is 1.05-1:1.
Preferably, the reaction temperature is-78-normal temperature, and the reaction pressure is normal pressure.
At present, the catalyst used for ethylene oligomerization is a mononuclear catalyst, and the reaction mechanism is as follows: (1) the catalytic active center metal reacts with two molecules of ethylene to form a five-membered ring intermediate; (2) reacting the five-membered ring intermediate with a molecule of ethylene to form a seven-membered ring intermediate; (3) the seven-membered ring intermediate continuously reacts with one molecule of ethylene to form a nine-membered ring intermediate; (4) the nine-membered ring intermediate undergoes elimination reaction to form 1-octene. As shown in fig. 1:
in this process, a number of side reactions are accompanied, for example: (1) the seven-membered ring intermediate undergoes elimination reaction to form 1-hexene; (2) the nine membered ring intermediate continues to react with one molecule of ethylene, eliminating the formation of 1-decene, and even continuing to produce dodecene, tetradecane, and higher olefins. The energy difference between these cyclic intermediates is not large, and thus it is difficult to avoid these side reactions.
The binuclear catalyst in the invention has the following reaction mechanism: (1) each metal forms a five-membered ring intermediate with two molecules of ethylene; (2) the two five-membered rings are connected with each other to form a large ring; (3) eliminating the formation of 1-octene, and improving the selectivity of 1-octene through the combined action of two active metal centers in the catalyst. The reaction principle is schematically shown in figure 2:
in the invention, the ligand with a specific structure is designed, so that the catalyst is easy to form a required binuclear structure; and the ligand contains a plurality of coordination sites, and after the ligand is coordinated with chromium metal, the redundant coordination sites interact with the cocatalyst, so that the activity of the catalyst is improved.
In the invention, the cocatalyst is alkyl aluminoxane or modified alkyl aluminoxane, and is selected from one or more of methyl aluminoxane and modified methyl aluminoxane.
In the invention, the molar ratio of Al to Cr in the cocatalyst is 100:1-1000:1.
The invention also provides application of the catalyst in ethylene selective oligomerization.
Further, the reaction may be carried out in a stainless steel reaction vessel. Adding a dehydrated and deoxidized reaction solvent and a cocatalyst under an inert gas atmosphere, stirring, adding the binuclear chromium catalyst of the invention after the temperature is constant, introducing hydrogen to 0.1-0.8Mpa, continuously introducing ethylene, maintaining the pressure of a reaction kettle to 2-5Mpa, and reacting for 10-30 min at 40-70 ℃. Then, closing an ethylene air inlet valve, cooling, decompressing and discharging the kettle to obtain an ethylene tetramerization product.
Before ethylene selective oligomerization, the reaction kettle is heated to 110-130 deg.C, vacuumized, replaced by nitrogen, cooled to room temperature and then added with reaction solvent and cocatalyst.
In the present invention, the initial concentration of the binuclear chromium-based catalyst in the reaction system is 0.1 to 0.11mmol/L.
Further, the oligomerization solvent is one or more of cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane and n-heptane.
The invention provides a new ethylene selective oligomerization catalyst, which adopts a binuclear structure, and has simple structure and catalytic activity of more than or equal to 10 multiplied by 10 6 g product/(molCr.h), the 1-octene selectivity can be more than 85%, the selectivity is high, and the method has industrial application prospect.
Drawings
FIG. 1 is a schematic diagram of the present ethylene oligomerization mononuclear catalysis principle.
FIG. 2 is a schematic illustration of the catalytic principle of the binuclear chromium catalyst of the present invention.
Detailed Description
The process according to the invention is further illustrated by the following specific examples, but the invention is not limited to the examples listed but encompasses any other known modifications within the scope of the claims.
Gas Chromatography (GC): model Agilent WAX 1701.42249; the carrier gas is high-purity nitrogen; the sample injection mode is an automatic sample injector; the nitrogen flow is 64.5ml/min; the temperature of the vaporization chamber is 280 ℃; split sample introduction, wherein the split ratio is 1:40; the sample injection amount is 0.2 mu l; the column flow rate was 1.5ml/min; the column temperature is first-order programmed temperature, the initial temperature is 50 ℃, the temperature is kept for 2 minutes, then the temperature is increased to 200 ℃ at the speed of 10 ℃/min, and the temperature is kept for 15 minutes; the detector temperature was 300 ℃; the external standard method is selected for quantification and is used for quantitative analysis of 1-octene, 1-hexene and other oligomerization short-chain products.
The raw material sources are as follows:
PCl 2 (NEt 2 ) (CAS 1069-08-5) Shanghai Jizhi Biochemical Co., ltd
CrCl 3 (THF) 3 (10170-68-0) Shanghai Jizhi Biochemical Co., ltd
Catalyst preparation
Preparation of bis (2-furyl) phosphine chloride: furan (0.5 mol) was dissolved in 300mL diethyl ether under nitrogen and cooled to-78 ℃. To this was slowly added dropwise a butyllithium solution (0.4 mol) over a period of 2h. After the completion of the dropwise addition, the reaction was continued at room temperature for 2 hours. The resulting reaction solution was cooled to 0℃and PCl was slowly added thereto 2 (NEt 2 ) (0.2 mol). After the addition, the reaction was continued at 0℃for 14 hours. HCl solution (0.44 mol) was added to the reaction mixture, and the reaction was continued for 3 hours after the completion of the addition. The reaction solution was filtered, and the light component was removed from the filtrate to obtain a crude product as a red oil. The crude product was distilled under reduced pressure to give a colorless oily product in 51% yield. 1 H-NMR(400MHz,25℃,CD 2 Cl 2 ):δ＝7.80ppm(dd,2H, 3 J HH ＝2.0Hz, 4 J HH ＝0.8Hz),7.07-7.06(m,2H),6.54-6.52(m,2H). 31 P{ 1 H}-NMR(162MHz,25℃,CD 2 Cl 2 ):δ＝17.84ppm(s)。
Ligand 1 preparation:
bis (2-furyl) phosphine chloride (0.1 mol) was dissolved in 100ml of THF under nitrogen protection, cooled to-78℃and a solution of butyllithium (0.11 mol) was added dropwise thereto, and reacted at-78℃for 2 hours. After the completion of the reaction, a tetrahydrofuran solution (0.06 mol) of 1, 3-dibromopropane was added dropwise thereto, and the reaction was returned to room temperature after the completion of the addition, and the reaction was continued for 2 hours. And after the reaction is finished, removing the solvent to obtain a crude product. The crude product is extracted by methylene dichloride, and the extract is concentrated, crystallized and purified to obtain the white solid of the ligand 1, and the yield is 85%. 1 H-NMR(400MHz,25℃,CD 2 Cl 2 ):δ＝7.75ppm(dd,4H, 3 J HH ＝2.0Hz, 4 J HH ＝0.8Hz),7.06-7.02(m,4H),6.54-6.52(m,4H),1.42-1.39(m,6H). 31 P{ 1 H}-NMR(162MHz,25℃,CD 2 Cl 2 ):δ＝25.28ppm(s)。
Ligand 2 preparation: according to the preparation method of the ligand 1, 3-dibromopropane is replaced by 1, 4-dibromobutane, so that the ligand 2 is obtained in a yield of 87%. 1 H-NMR(400MHz,25℃,CD 2 Cl 2 ):δ＝7.75ppm(dd,4H, 3 J HH ＝2.0Hz, 4 J HH ＝0.8Hz),7.06-7.02(m,4H),6.54-6.52(m,4H),1.42-1.38(m,8H). 31 P{ 1 H}-NMR(162MHz,25℃,CD 2 Cl 2 ):δ＝25.15ppm(s)。
Ligand 3 preparation: according to the preparation method of the ligand 1, 3-dibromopropane is replaced by 1, 5-dibromopentane, so that the ligand 3 is obtained with the yield of 88%. 1 H-NMR(400MHz,25℃,CD 2 Cl 2 ):δ＝7.75ppm(dd,4H, 3 J HH ＝2.0Hz, 4 J HH ＝0.8Hz),7.06-7.02(m,4H),6.54-6.52(m,4H),1.42-1.38(m,8H),1.29-1.28(m,2H). 31 P{ 1 H}-NMR(162MHz,25℃,CD 2 Cl 2 ):δ＝25.11ppm(s)。
Catalyst 1 preparation: chromium trichloride tetrahydrofuran complex (10 mmol) was added to THF under nitrogen protection, stirred and suspended, and cooled to 0 ℃. A solution of ligand 1 (10 mmol) in THF was added dropwise thereto, and the reaction was continued at 0℃for 2 hours after completion of the dropwise addition. The reaction was allowed to return to room temperature and reacted for 2 hours. The temperature was raised to 50℃and the reaction was continued for 2h. And after the reaction is finished, concentrating the reaction liquid to obtain a crude catalyst product. The crude product was recrystallized from tetrahydrofuran/hexane to give catalyst 1.
Catalyst 2 preparation: according to the preparation method of the catalyst 1, the ligand 1 is replaced by the ligand 2, so as to obtain the catalyst 2.
Catalyst 3 preparation: according to the preparation method of the catalyst 1, the ligand 1 is replaced by the ligand 3, so as to obtain the catalyst 3.
Example 1
Heating a 2L reaction kettle to 110-130 ℃, vacuumizing for 2-4h, replacing nitrogen for three times during the period, cooling to room temperature, adding 1L of dehydrated and deoxidized methylcyclohexane and quantitative modified methylaluminoxane, stirring, adding quantitative catalyst 1 after the temperature is constant, introducing hydrogen to 0.5Mpa, continuously introducing ethylene, maintaining the pressure of the reaction kettle to 5MPaG, and reacting for 20min at 40 ℃. Then, the ethylene inlet valve is closed, the temperature is rapidly reduced by using a low-temperature circulating water bath, the pressure is slowly released, the kettle is discharged to obtain an ethylene oligomerization product, and the addition amounts of the catalyst and the modified methylaluminoxane are shown in the table 1.
Examples 2 to 9
Oligomerization was performed under different conditions as in example 1, the reaction conditions being shown in table 1.
Comparative example 1
The bis (2-furyl) phosphine chloride and chromium trichloride tetrahydrofuran complex are directly added into oligomerization without preparing a catalyst in advance.
Heating a 2L reaction kettle to 110-130 ℃, vacuumizing for 2-4h, replacing nitrogen for three times during the period, cooling to room temperature, adding 1L of dehydrated and deoxidized methylcyclohexane and quantitative methyl aluminoxane, stirring, adding quantitative bis (2-furyl) phosphine chloride and chromium trichloride tetrahydrofuran complex after the temperature is constant, introducing hydrogen to 0.5Mpa, continuously introducing ethylene, maintaining the pressure of the reaction kettle to 5MPa, and reacting for 20min at 40 ℃. Then, the ethylene inlet valve is closed, the temperature is quickly reduced by using a low-temperature circulating water bath, the pressure is slowly released, and the kettle is discharged to obtain an ethylene oligomerization product. The addition of ligand 1 and chromium trichloride tetrahydrofuran complex is shown in Table 1.
Comparative example 2
Using ligand 4, the structure isLigand 4 and chromium trichloride tetrahydrofuran complex were added directly to the oligomerization reaction.
Oligomerization of ethylene: before the reaction, heating the reaction kettle to 110-130 ℃, vacuumizing for 2-4h, replacing nitrogen for three times during the period, cooling to room temperature, adding dehydrated and deoxidized methylcyclohexane and quantitative methyl aluminoxane, stirring, after the temperature is constant, adding quantitative ligand 4 and chromium trichloride tetrahydrofuran complex, introducing hydrogen to 0.5Mpa, continuously introducing ethylene, maintaining the pressure of the reaction kettle to 5MPa, and reacting for 20min at 40 ℃. Then, the ethylene inlet valve is closed, the temperature is quickly reduced by using a low-temperature circulating water bath, the pressure is slowly released, and the kettle is discharged to obtain an ethylene oligomerization product. The amount of ligand 4 and chromium trichloride tetrahydrofuran complex added is shown in Table 1.
The reaction results of examples and comparative examples are shown in Table 2.
TABLE 1 reaction conditions for examples 1-9 and comparative examples 1-2
TABLE 2 reaction results for examples 1-9 and comparative examples 1-3
1-C6 represents 1-hexene, other C6 represents alkane/alkene having 6 carbon atoms except 1-C6, 1-C8 represents 1-octene, C4+C10+ represents alkane/alkene having 4 and more than 10 carbon atoms, and PE represents polymer.
All modifications and equivalent substitutions to the technical proposal of the invention are included in the protection scope of the invention without departing from the scope of the technical proposal of the invention.

Claims (10)

1. The ethylene oligomerization catalyst is characterized by comprising a binuclear chromium catalyst and a cocatalyst, wherein the binuclear chromium catalyst has the following structure:
n is 1 to 3.
2. The catalyst of claim 1, wherein the binuclear chromium catalyst is prepared by reacting a biphosphine ligand with a chromium source;
preferably, the structure of the biphosphine ligand is as follows:n is 1-3;
preferably, the chromium source is tetrahydrofuran chromium chloride or chromium chloride;
preferably, the reaction is carried out in a solvent selected from tetrahydrofuran, methyltetrahydrofuran.
3. The catalyst according to claim 1 or 2, wherein the biphosphine ligand is prepared by reacting a difuranyl phosphine chloride shown in formula I with a dibromoalkane shown in formula II under the action of alkyl lithium;
wherein the structural formula of the difuranyl phosphine chloride shown in the formula I is
The dibromoalkane shown in the formula II has the structural formula of
n is 1 to 3.
4. The catalyst according to claim 3, wherein the molar ratio of dibromoalkane represented by formula II to difuranyl phosphine chloride represented by formula I is 0.5-0.6:1, and the molar ratio of alkyl lithium to difuranyl phosphine chloride represented by formula I is 1.05-1:1.
5. The catalyst of any of claims 1-4 wherein the molar ratio of bisphosphine ligand to chromium in the chromium source is from 1:1 to 1:1.1.
6. The catalyst according to any one of claims 1 to 5, wherein the reaction temperature is 0 to 50 ℃ and the reaction pressure is normal pressure.
7. The catalyst according to any one of claims 1 to 6, wherein the cocatalyst is an alkylaluminoxane or a modified alkylaluminoxane, and is one or more selected from methylaluminoxane and modified methylaluminoxane;
preferably, the molar ratio of Al to Cr in the cocatalyst is 100:1:1000:1.
8. Use of a catalyst according to any one of claims 1 to 7 in the selective oligomerization of ethylene.
9. The use according to claim 8, wherein the ethylene selective oligomerization is prepared by: adding a dehydrated and deoxidized reaction solvent and a cocatalyst under an inert gas atmosphere, stirring, adding the binuclear chromium-based catalyst according to any one of claims 1-8 after the temperature is constant, introducing hydrogen to 0.1-0.8Mpa, continuously introducing ethylene, maintaining the pressure of a reaction kettle to 2-5Mpa, and reacting at 40-70 ℃ for 10-30 min.
10. The use according to claim 9, characterized in that the initial concentration of the binuclear chromium-based catalyst in the reaction system is 0.1 to 0.11mmol/L.
CN202311306822.8A 2023-10-10 2023-10-10 Ethylene oligomerization catalyst and application thereof Pending CN117563674A (en)

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