CN115672406A - High-temperature-resistant ethylene tetramerization catalyst and application thereof - Google Patents

High-temperature-resistant ethylene tetramerization catalyst and application thereof Download PDF

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CN115672406A
CN115672406A CN202211388143.5A CN202211388143A CN115672406A CN 115672406 A CN115672406 A CN 115672406A CN 202211388143 A CN202211388143 A CN 202211388143A CN 115672406 A CN115672406 A CN 115672406A
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CN115672406B (en
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吕英东
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Wanhua Chemical Group Co Ltd
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Abstract

The invention provides a high-temperature-resistant ethylene tetramerization catalyst, which comprises a chromium source, a cocatalyst and a ligand, and is characterized in that the ligand has the structure as follows:
Figure DDA0003930842540000011
x represents hydrogen or a residue of an amino acid, and n is 0 to 2; z represents H or HN (R) 1 )(R 2 )(R 3 ) Wherein R is 1 、R 2 、R 3 Each represents the same or different alkyl group having 1 to 6 carbon atoms. The method prepares 1-octene by tetramerization of ethylene at high selectivity at high temperature by using chromium-based catalyst system, wherein the chromium-based catalyst comprises chromium sourceA cocatalyst and a ligand with a P-N-P skeleton structure containing carboxyl.

Description

High-temperature-resistant ethylene tetramerization catalyst and application thereof
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a high-temperature-resistant ethylene tetramerization catalyst and application thereof.
Background
1-octene is used as an important organic raw material and a chemical intermediate, and is mainly used for producing high-end PE and POE and used as a raw material for producing plasticizers, alcohols for detergents and lubricating oil additives. Ethylene tetramerization is one of the main methods for preparing linear 1-octene industrially at present, and is a hotspot of research in recent years because the product quality is high, and the method can better adapt to market demands.
The technicians of Sasol company (patent WO 2004/056478) use PNP ligand, chromium acetylacetonate and MAO to form a catalytic system, so as to realize ethylene tetramerization, achieve the selectivity of 1-octene in the product of 70%, and realize the industrial production of ethylene tetramerization.
In the industrial production process of ethylene tetramer, the problem that the device is stopped because a high polymer ethylene byproduct is generated to block a pipeline exists, and the device is difficult to stably operate for a long period because the high polymer ethylene must be periodically stopped and cleaned.
The reason why the high polymer of ethylene blocks the pipeline is that the reaction temperature is low, usually 40-60 ℃, and the high polymer has low solubility in the reaction system and is precipitated. The existing catalyst system is inactivated under the high-temperature condition, and the problem of blockage can not be solved by increasing the reaction temperature and increasing the solubility of high polymer.
In order to overcome the defects in the existing production process, a novel catalyst needs to be developed, so that the ethylene tetramerization reaction can be carried out at a higher temperature, and more byproducts can not be produced, thereby solving the problem of equipment pipeline blockage.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant ethylene tetramerization catalyst and application thereof, and the method enables ethylene to carry out tetramerization reaction at high selectivity at a high temperature by using a chromium catalyst system so as to prepare 1-octene.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high temperature resistant ethylene tetramerization catalyst comprises a chromium source, a cocatalyst and a ligand, wherein the ligand has the structure:
Figure BDA0003930842530000021
x represents hydrogen or amino acid residue (amino acid residue refers to the residue of amino acid except CH (COOH) (NH 2)), preferably-H, -CH 3 、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-CH 2 (C 6 H 5 )、-CH 2 (C 6 H 4 )OH、-CH 2 CH 2 COOH、-(CH 2 ) 4 NH 2 、-CH 2 CH 2 CONH 2 、CH 2 CH 2 SCH 3 、-CH 2 OH、-CH 2 SH；
n is 0 to 2;
z represents H or HN (R) 1 )(R 2 )(R 3 ) Wherein R is 1 、R 2 、R 3 Each represents the same or different alkyl group having 1 to 6 carbon atoms; preferably H, HNEt 3 ；
Preferably, the ligand is prepared by reacting amino acid with diphenyl phosphorus chloride; the method comprises the following specific steps: mixing amino acid and diphenyl phosphorus chloride in a solvent according to a molar ratio of 1.8-2.2, cooling the mixed solution to-5 ℃, optionally dropping organic amine into the mixed solution, keeping the mixed solution at-5 ℃ for reaction for 0.5-2 h after dropping is finished, and then heating to 25-35 ℃ for reaction for 1-4 h. Obtaining a ligand after post-treatment and purification;
in the present invention, various natural amino acids may be used as the amino acid, and an unnatural amino acid such as β -aminopropionic acid may also be used.
Preferably, the amino acid is selected from one or more of glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, tyrosine, glutamic acid, lysine, methionine, cysteine, beta-aminopropionic acid;
preferably, the solvent is an aprotic solvent, including one or more of dichloromethane, tetrahydrofuran, acetone, DMF; particularly preferably, the solvent is dichloromethane;
preferably, the organic amine is N (R) 1 )(R 2 )(R 3 ) Wherein R is 1 、R 2 、R 3 Respectively represent the same or different alkyl groups with 1 to 6 carbon atoms; preference for NEt 3 ；
Preferably, the addition amount of the organic amine is 2 to 5 times of the molar amount of the amino acid.
Preferably, the chromium source is selected from one or more of chromium chloride, chromium tri (tetrahydrofuran) trichloride, chromium (III) 2-ethylhexanoate, chromium acetylacetonate and chromium hexacarbonyl;
PNP ligands adopted by Sasol company are neutral ligands, and the ligands and the central metal Cr form the catalyst only through coordination. This coordination is destroyed under high temperature conditions and the ligand dissociates from the metal, resulting in catalyst failure.
In the invention, carboxyl anion is introduced on the P-N-P ligand skeleton, so that the ligand and the central metal have electrostatic interaction besides coordination, the combination of the ligand and the central metal is enhanced, and the catalyst can tolerate higher temperature.
In the invention, the cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, methylaluminoxane, modified methylaluminoxane and ethylaluminoxane; methylaluminoxane or modified methylaluminoxanes are preferred.
In the present invention, the molar ratio of the ligand to Cr is 1 to 10, preferably 2.
In the present invention, the molar ratio of Al to Cr in the cocatalyst is 100: -1000, preferably 200.
The invention also provides the application of the catalyst in ethylene tetramerization reaction.
The ligand, the chromium source and the cocatalyst can be mixed and prepared into a catalyst in advance and then added into the ethylene oligomerization reaction, or can be added in the oligomerization reaction process respectively without preparation in advance.
Furthermore, the catalyst of the invention is used in ethylene tetramerization reaction, and the reaction can be carried out in a stainless steel reaction kettle. Firstly, heating a reaction kettle to 110-130 ℃ before reaction, vacuumizing for 2-4h, replacing nitrogen for three times, cooling to room temperature, adding a dehydrated and deoxidized reaction solvent and a cocatalyst, stirring, adding a ligand and a chromium source after the temperature is constant, and reacting at the temperature of 40-120 ℃ and the pressure of 2-6 MPaG. Then, closing the ethylene inlet valve, rapidly cooling by using a low-temperature circulating water bath, slowly releasing pressure, and unloading the kettle to obtain an ethylene tetramerization product.
Further, the mass concentration of the chromium source in the system is 5-15 mu mol/L in terms of chromium atoms.
Further, the reaction time of ethylene tetramerization is 10min-60min.
Further, the reaction solvent is one or more of n-pentane, cyclopentane, methylcyclopentane, methylene cyclopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane and isooctane, and methylcyclohexane is preferred.
Compared with the prior art, the method has the advantages that the high-temperature resistance of the catalyst is excellent, the blockage of polymer on equipment pipelines can be effectively reduced, the high selectivity of 1-octene at 120 ℃ can be maintained, and the content of polymer is low.
Detailed Description
The process of the present invention is further illustrated by the following specific examples, but the invention is not limited to the examples listed, but also encompasses any other known modifications within the scope of the claims of the invention.
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-flow sample injection is carried out, and the split-flow ratio is 1; the sample injection amount is 0.2 mul; the column flow rate was 1.5ml/min; the column temperature is first-order temperature programming, the initial temperature is 50 ℃, the temperature is kept for 2 minutes, then the temperature is increased to 250 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 minutes; the temperature of the detector is 300 ℃; an external standard method is selected for quantification and is used for quantitatively analyzing 1-octene, 1-hexene and other short chain oligomerization products.
Nuclear magnetic analysis (NMR): model Bruke Fourier 300. And (3) performing qualitative analysis on the ligand.
Preparation of PNP ligand 1
Figure BDA0003930842530000051
Under the protection of nitrogen, glycine (0.1 mol) and diphenyl phosphorus chloride (0.21 mol) are added into 100mL dichloromethane, stirred, cooled to-5 ℃, added with triethylamine (0.5 mol), kept at-5 ℃ for reaction for 1h, and heated to 35 ℃ for reaction for 1h. And after the reaction is finished, filtering while the reaction is hot, and removing the solvent from the filtrate to obtain a crude product solid. The crude product was purified by column chromatography (eluent was a mixture of methanol and ethyl acetate in a volume ratio of 1. 31 P NMR：δ(CDCl3)：46.8(s)。
Preparation of PNP ligand 2
Figure BDA0003930842530000061
Under the protection of nitrogen, alanine (0.1 mol) and diphenyl phosphorus chloride (0.21 mol) are added into 100mL dichloromethane, stirred, cooled to 0 ℃, added with tripropylamine (0.4 mol), kept at 0 ℃ for reaction for 0.5h, and heated to 25 ℃ for reaction for 4h. And after the reaction is finished, filtering while the solution is hot, and removing the solvent from the filtrate to obtain a crude product solid. The crude product was purified by column chromatography (eluent was a mixture of methanol and ethyl acetate in a volume ratio of 1. 31 P NMR：δ(CDCl3)：46.2(s)。
Preparation of PNP ligand 3
Figure BDA0003930842530000062
Under the protection of nitrogen, adding beta-aminopropionic acid (0.1 mol) and diphenyl phosphorus chloride (0.21 mol) into 100mL of dichloromethane, stirring, cooling to 5 ℃, adding N, N-diethylmethylamine (0.2 mol), reacting for 2h while maintaining the temperature at 5 ℃, and heating to 30 ℃ for reacting for 2h. After the reaction, 1N diluted hydrochloric acid is dripped into the reaction liquid until the pH value is 6.5, the mixture is filtered while the mixture is hot, and the solvent is removed from the filtrate to obtain a crude product solid. The crude product was purified by column chromatography (eluent was a mixture of methanol and ethyl acetate in a volume ratio of 1. 31 P NMR：δ(CDCl3)：49.8(s)。
Preparation of PNP ligand 4
Figure BDA0003930842530000071
Under the protection of nitrogen, valine (0.1 mol) and diphenyl phosphorus chloride (0.21 mol) are added into 100mL dichloromethane, stirred, cooled to 0 ℃, added with trihexylamine (0.3 mol), kept at 0 ℃ for reaction for 1h, and heated to 30 ℃ for reflux reaction for 3h. And after the reaction is finished, filtering while the solution is hot, and removing the solvent from the filtrate to obtain a crude product solid. The crude product was purified by column chromatography (eluent was a mixture of methanol and ethyl acetate in a volume ratio of 1. 31 P NMR：δ(CDCl3)：45.5(s)。
Comparative PNP ligand preparation
Figure BDA0003930842530000072
Under the protection of nitrogen, isopropylamine (0.1 mol) and diphenyl phosphorus chloride (0.21 mol) are added into 100mL dichloromethane, stirred, cooled to-5 ℃, added with triethylamine (0.5 mol), kept at-5 ℃ for reaction for 1h, and then heated to 35 ℃ for reaction for 1h. And after the reaction is finished, filtering while the solution is hot, and removing the solvent from the filtrate to obtain a crude product solid. The crude product was purified by column chromatography (eluent was a mixture of methanol and ethyl acetate in a volume ratio of 1. 31 P NMR：δ(CDCl3)：48.2(s)。
Example 1
Before reaction, a 500mL reaction kettle is heated to 120 ℃, vacuumized for 2h, nitrogen is replaced for three times during the process, after the temperature is cooled to room temperature, 100mL dehydrated and deoxidized methylcyclohexane and modified methylaluminoxane (0.5 mmol Al) are added, stirring is carried out, ligand 1 (1 mu mol) and chromium trichloride (1 mu mol) are added, and reaction is carried out at the temperature of 40 ℃ and the pressure of 6MPaG for 10min. Then, closing the ethylene inlet valve, rapidly cooling by using a low-temperature circulating water bath, slowly releasing pressure, and unloading the kettle to obtain an ethylene tetramerization product. The polymer by-product was collected by filtration, dried overnight and weighed. The selectivity and activity were calculated from the GC analytical data and polymer mass. The results are shown in Table 1.
Example 2
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized n-heptane and methylaluminoxane (1 mmol of Al) were added thereto, followed by stirring, addition of ligand 2 (10. Mu. Mol) and chromium acetylacetonate (1. Mu. Mol), and reaction at 40 ℃ and a pressure of 5MPaG for 10min.
Example 3
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized isooctane and methylaluminoxane (0.1 mmol of Al) were added, stirred, added with ligand 3 (2. Mu. Mol) and tris (tetrahydrofuran) chromium trichloride (1. Mu. Mol), reacted at 60 ℃ under a pressure of 4MPaG for 20min.
Example 4
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized n-hexane and modified methylaluminoxane (0.2 mmol of Al) were added, stirred, added with ligand 4 (5. Mu. Mol) and chromium 2-ethylhexanoate (1. Mu. Mol), and reacted at 60 ℃ under a pressure of 3MPaG for 20min.
Example 5
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized cyclohexane and modified methylaluminoxane (0.3 mmol of Al) are added, stirred, added with ligand 4 (3 mu mol) and tris (tetrahydrofuran) chromium trichloride (1 mu mol), reacted at the temperature of 80 ℃ and the pressure of 2MPaG for 20min.
Example 6
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized methylcyclohexane and modified methylaluminoxane (0.3 mmol of Al) were added, stirred, added with ligand 4 (4. Mu. Mol) and chromium 2-ethylhexanoate (1. Mu. Mol), reacted at 80 ℃ under a pressure of 2MPaG for 30min.
Example 7
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized methylcyclohexane and modified methylaluminoxane (0.2 mmol of Al) are added, stirred, added with ligand 2 (2. Mu. Mol) and chromium trichloride (1. Mu. Mol), and reacted at 100 ℃ and a pressure of 3MPaG for 30min.
Example 8
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized methylcyclohexane and modified methylaluminoxane (0.3 mmol of Al) were added, stirred, added with ligand 1 (3. Mu. Mol) and chromium acetylacetonate (0.9. Mu. Mol), and reacted at a temperature of 100 ℃ and a pressure of 4MPaG for 20min.
Example 9
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized methylcyclohexane and modified methylaluminoxane (0.3 mmol of Al) were added, stirred, added with ligand 3 (4. Mu. Mol) and chromium 2-ethylhexanoate (1.1. Mu. Mol), and reacted at 120 ℃ under a pressure of 5MPaG for 10min.
Example 10
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized methylcyclohexane and modified methylaluminoxane (0.3 mmol of Al) were added, and the mixture was stirred, and ligand 2 (5. Mu. Mol) and chromium trichloride (1. Mu. Mol) were added to react at 120 ℃ under a pressure of 6MPaG for 20 minutes.
Comparative example 1
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized methylcyclohexane and modified methylaluminoxane (0.3 mmol of Al) were added, stirred, added with comparative ligand 5 (4. Mu. Mol) and chromium 2-ethylhexanoate (1. Mu. Mol), and reacted at 120 ℃ under a pressure of 5MPaG for 10min.
Comparative example 2
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized methylcyclohexane and modified methylaluminoxane (0.3 mmol of Al) were added, stirred, added with comparative ligand 5 (3. Mu. Mol) and chromium acetylacetonate (1. Mu. Mol), and reacted at a temperature of 100 ℃ and a pressure of 4MPaG for 20min.
Comparative example 3
The procedure of example 1 was followed except that: 100mL of dehydrated and deoxidized cyclohexane and modified methylaluminoxane (0.3 mmol of Al) are added, stirred, added with a contrast ligand 5 (3 mu mol) and tris (tetrahydrofuran) chromium trichloride (1 mu mol), reacted at a temperature of 80 ℃ and a pressure of 2MPaG for 20min.
The experimental results of the examples and comparative examples are shown in Table 1.
TABLE 1
Figure BDA0003930842530000111
The technical scheme of the invention is to be modified or replaced equivalently without departing from the scope of the technical scheme of the invention, and the technical scheme of the invention is covered by the protection scope of the invention.

Claims (8)

1. A high-temperature-resistant ethylene tetramerization catalyst comprises a chromium source, a cocatalyst and a ligand, and is characterized in that the ligand has the structure as follows:
Figure FDA0003930842520000011
x represents hydrogen or a residue of an amino acid, preferably-H, -CH 3 、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-CH 2 (C 6 H 5 )、-CH 2 (C 6 H 4 )OH、-CH 2 CH 2 COOH、-(CH 2 ) 4 NH 2 、-CH 2 CH 2 CONH 2 、CH 2 CH 2 SCH 3 、-CH 2 OH、-CH 2 SH；
n is 0 to 2;
z represents H or HN (R) 1 )(R 2 )(R 3 ) Wherein R is 1 、R 2 、R 3 Respectively represent the same or different alkyl groups with 1 to 6 carbon atoms; preferably H, HNEt 3 。
2. The catalyst according to claim 1, wherein the ligand is prepared by reacting an amino acid with diphenyl phosphonium chloride; the method specifically comprises the following steps: mixing amino acid and diphenyl phosphorus chloride in a solvent according to a molar ratio of 1.8-2.2, cooling the mixed solution to-5 ℃, optionally dripping organic amine into the mixed solution, keeping the temperature of-5 ℃ for reaction for 0.5-2 h after dripping is finished, heating to 25-35 ℃ for reaction for 1-4 h, and performing post-treatment and purification to obtain the ligand.
3. The catalyst according to claim 1, wherein, preferably, the amino acid is selected from one or more of glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, tyrosine, glutamic acid, lysine, methionine, cysteine, beta-aminopropionic acid;
preferably, the solvent is an aprotic solvent, including one or more of dichloromethane, tetrahydrofuran, acetone, DMF; more preferably, the solvent is dichloromethane.
4. Catalyst according to claim 1, characterized in that the organic amine is N (R) 1 )(R 2 )(R 3 ) Wherein R is 1 、R 2 、R 3 Each represents the same or different alkyl group having 1 to 6 carbon atoms; preference for NEt 3 ；
Preferably, the addition amount of the organic amine is 2 to 5 times of the molar amount of the amino acid.
Preferably, the chromium source is selected from one or more of chromium chloride, chromium tri (tetrahydrofuran) trichloride, chromium (III) 2-ethylhexanoate, chromium acetylacetonate and chromium hexacarbonyl.
5. The catalyst according to any one of claims 1 to 4, wherein the cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, methylaluminoxane, modified methylaluminoxane and ethylaluminoxane; methylaluminoxane or modified methylaluminoxanes are preferred.
In the present invention, the molar ratio of the ligand to Cr is 1 to 10, preferably 2.
In the present invention, the molar ratio of Al to Cr in the cocatalyst is 100: -1000, preferably 200.
6. Use of a catalyst according to any one of claims 1 to 5, wherein the catalyst is used in an ethylene tetramerisation reaction.
7. Use according to claim 6, wherein the ligand, the chromium source and the cocatalyst are mixed and added to the ethylene oligomerization reaction in advance, or are added separately during the oligomerization reaction without prior preparation.
8. Use according to claim 6 or 7, for the preparation of ethylene tetramerisation by: heating the reaction kettle to 110-130 ℃ before reaction, vacuumizing for 2-4h, replacing nitrogen for three times during the reaction, cooling to room temperature, adding a dehydrated and deoxidized reaction solvent and a cocatalyst, stirring, adding a ligand and a chromium source after the temperature is constant, and reacting at 40-120 ℃ and under the pressure of 2-6 MPaG; then, closing an ethylene inlet valve, rapidly cooling by using a low-temperature circulating water bath, slowly releasing pressure, and unloading the kettle to obtain an ethylene tetramerization product;
preferably, the reaction time of ethylene tetramerization is 10min-60min;
preferably, the reaction solvent is one or more of n-pentane, cyclopentane, methylcyclopentane, methylene cyclopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane and isooctane.
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