CN115501916A - Catalyst composition for ethylene trimerization and application thereof - Google Patents

Catalyst composition for ethylene trimerization and application thereof Download PDF

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CN115501916A
CN115501916A CN202211159113.7A CN202211159113A CN115501916A CN 115501916 A CN115501916 A CN 115501916A CN 202211159113 A CN202211159113 A CN 202211159113A CN 115501916 A CN115501916 A CN 115501916A
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ethylene
trimerization
alkyl aluminum
catalyst composition
chromium
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CN115501916B (en
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刘惠
罗清红
薛丽丽
徐人威
武大庆
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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Abstract

The invention discloses a catalyst composition for ethylene trimerization, which consists of a chromide, a phosphonyl compound, an alkyl aluminum auxiliary agent and an inorganic phosphorus-containing halide depolymerizing agent, wherein the chromide is chromium isooctanoate, chromium acetylacetonate or tetrahydrofuran chromium chloride, and the alkyl aluminum auxiliary agent is triethyl aluminum, methylaluminoxane, trimethyl aluminum or isobutyl aluminum; the electron donor is inorganic phosphorus-containing halide depolymerizing agent. Under the condition that two main components of a chromium catalyst and an alkyl aluminum cocatalyst are not changed, inorganic phosphorus-containing halide is used as a depolymerizing agent for the first time, has proper electron donating capability, can be combined with an alkyl aluminum reagent to prevent the aggregation of the alkyl aluminum reagent, does not influence the reduction capability of the alkyl aluminum reagent, and meanwhile pentaphenylphosphine pyrrole is used for replacing a pyrrole compound as a ligand, so that an ethylene trimerization composition formed by the pentaphenylphosphine pyrrole and the pyrrole compound has excellent ethylene trimerization catalytic performance.

Description

Catalyst composition for ethylene trimerization and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst composition for ethylene trimerization and application thereof.
Background
Linear alpha-olefin (LAO) is an important organic chemical raw material and intermediate, can be used for producing comonomers of high-density polyethylene, linear low-density polyethylene and polyolefin elastomer, and can also be used for producing raw materials of fine chemicals such as high-end fully synthetic lubricating oil, surfactant, plasticizer and the like. Advanced and mature LAO production technology is mainly mastered in Chevron Phillips, shell, sasol, idemitsu, SABIC/Linde, INEOS and other globally known enterprises. China has started to move relatively late in the field and is still in the development stage overall. The foreign advanced technology is used for Chinese blockade, and China cannot introduce mature LAO production process, so that the significance of independently developing the localization technology is great.
Petrochemical 2-butene isomerization has already realized the industrialization of 1-butene at present, and Axens adopts ethylene dimerization to realize the industrialization of 1-butene. Four enterprises have been industrialized worldwide for trimerizing ethylene to prepare 1-hexene, which are Chevron Phillips, china petrochemicals, china Petroleum and Mitsui Chemicals. Only Sasol is currently industrialized worldwide. The 1-decene prepared by ethylene pentapolymerization is industrialized all over the world at present.
In recent years, with the widespread use of materials such as linear low density polyethylene, high density polyethylene, and polyolefin elastomers, the consumption of linear alpha-olefin (LAO) monomers such as 1-hexene and 1-octene used for synthesizing linear low density polyethylene has been increasing significantly. 2019 the yield of the alpha-olefin in China C5 and above is 7.5 ten thousand tons/year, the yield is 4.5 ten thousand tons, and the contribution is mainly from a 1-hexene project. Besides importing pure alpha-olefin, china imports a large amount of derivative products of the alpha-olefin, such as LLDPE/HDPE, PAO, POE and the like, every year, so that the consumption amount of the equivalent alpha-olefin and the external dependence are far larger than the above values.
1-hexene is used as an important organic raw material and a chemical intermediate, and is mainly used for producing high-end Polyethylene (PE). Compared with the 1-butene copolymer resin, the Linear Low Density Polyethylene (LLDPE) and the High Density Polyethylene (HDPE) which are produced by copolymerizing 1-hexene and ethylene have obvious advantages in the aspects of mechanical processing, heat resistance, flexibility, transparency and the like of polyethylene. Is particularly suitable for producing packaging films and agricultural covering films. The technology of Phillips company is successfully popularized worldwide, the selectivity of 1-hexene in the process of the company is higher than 90%, and the normal rate of 1-hexene is also higher than 92%. In 2007, yanshan petrochemical industry is built into the first 5-ten thousand-ton/year ten-thousand-ton grade 1-hexene device with independent intellectual property rights, the reaction temperature is 100-130oC, the pressure is 3-5MPa, the highest selectivity of 1-hexene can reach 93%, and the purity can reach 99.2%. In 2010, the medium petroleum develops a 2-ten thousand ton/year 1-hexene process package, and the process is built and put into production in 2014, the technology adopts a chromium-based catalyst, polymerization-grade ethylene is used as a raw material, the reaction temperature is 125 ℃ and the pressure is 5MPa, the highest selectivity of 1-hexene can reach 94%, and the purity of the product can reach 99%.
There are a number of patents on the selective trimerization of ethylene.
In 1999, phillips application US5856257 adopts a chromium catalyst to catalyze ethylene to perform selective trimerization reaction to generate 1-hexene with the selectivity as high as 95 percent, and the device process is the most advanced 1-hexene process technology in the world at present. In patent CN102558107A, crCl3 (THF) 3 is prepared quickly and efficiently by the petrochemical company of China through microwave radiation, the selectivity of 1-hexene produced by a chromium catalyst prepared on the basis is higher than 92 percent, the purity is as high as 99.2 percent, and the process is built into a 5-ten thousand ton/year 1-hexene production process in the petrochemical company of Beijing Yanshan in 2007.
EP0608447A1 of the Phillips application patent discloses that a halogen-containing compound promoter can greatly improve the activity and selectivity of a catalyst, wherein the halogen-containing compound promoter can be an inorganic halide or an organic halogen-containing compound, but the activity and the selectivity of the catalyst still do not meet the requirements of people.
JP 08134131 discusses the use of saturated halogenated hydrocarbons characterized by containing three or more halogen atoms on two adjacent carbon atoms at the ends as promoters for chromium isooctanoate, 2, 5-dimethylpyrrole and triethylaluminium catalysts, the four-component catalyst system having a significantly improved catalytic activity for the selective trimerization of ethylene to 1-hexene.
The catalyst system in patent CN1490291 applied by China oil and gas Co., ltd comprises chromium isooctanoate, 2,4-dimethylpyrrole, triethylaluminum, 1,2,3,4,5,6-hexachlorocyclohexane gamma body and the like, the selectivity of 1-hexene is as high as 99.3%, and the petroleum in the trimerization technology realizes the industrialization of 1-hexene in Daqing petrochemical company and Dushan petrochemical company in 2007 and 2014 respectively.
Mitsubishi chemical company, filed US08790479, discloses a process for the preparation of alpha-olefin oligomers by oligomerizing alpha-olefins in a reaction zone in the presence of a reaction solution containing a chromium-based catalyst, the catalyst composition being a source of chromium, a pyrrole derivative, an aluminum alkyl and an organic halide (tetrachloroethane).
Zhongyangshi patent CN 1108193C discloses a halogen-containing accelerator capable of accelerating selective trimerization of ethylene, which is an aromatic hydrocarbon or halogenated aromatic hydrocarbon compound at least containing one halogenated alkyl substituted by C1-2-alkyl substituted by at least two halogen atoms at alpha-position on the aromatic ring, and the addition of the accelerator can obviously improve the activity of the catalyst and the selectivity of 1-hexene.
It can be seen from the above that, in the selective ethylene trimerization catalyst, besides the chromium source, the alkyl aluminum and the ligand, the fourth component is a key factor influencing the activity and selectivity of the catalyst, and an excellent fourth component is developed, so that not only can the catalytic activity and the selectivity of a target product be improved, but also the generation of a polymer can be effectively reduced, and the process flow is simplified.
Disclosure of Invention
According to a large number of published patents or reports, the prior art still has the problems of low catalyst activity, high raw material cost, low 1-hexene selectivity, and small amount of polymer generated in the polymerization process, which affects the continuous operation of the device. In order to solve the problems, the invention provides a catalyst composition for ethylene trimerization, which consists of chromium metal salt, pentaphenyl phosphino, alkyl aluminum and a depolymerization reagent, wherein 1-hexene in a reaction product has high selectivity, and compared with the disclosed catalyst (pyrrole is used as a ligand), the catalyst composition has the advantages that the content of byproduct polyethylene is very low, and the catalyst composition has higher activity; the ethylene trimerization reaction can be carried out through in-situ polymerization in industrialization, and prepolymerization is not needed.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a catalyst composition for the trimerization of ethylene comprising the following components:
(1) Chromium compound: chromium isooctanoate, chromium acetylacetonate or chromium tetrahydrofuran chloride;
(2) Ligand: pentaphenylphosphinole, of the formula:
Figure 853294DEST_PATH_IMAGE001
；
(3) An alkyl aluminum assistant: triethylaluminum, methylaluminoxane, trimethylaluminum, or isobutylaluminum;
(4) Depolymerizing agent: PCl 3 、PCl 5 、PBr 5 Or PBr 3 。
Further, the mole ratio of the chromide, the pentaphenylphosphine pyrrole, the alkyl aluminum assistant and the depolymerizing agent is as follows: 1, 0.1 to 100, 1 to 1000; preferably 1.1 to 10; more preferably 1:1 to 8:1 to 100.
Further, the preparation method of the pentaphenylphosphine comprises the following steps: tolane (4.0 g,22 mmol) was dissolved in dry tetrahydrofuran (25 mL) and lithium turnings (140 mg,20 mmol) were added under argon. The reaction was stirred at room temperature overnight to give a dark green solution. Dichlorophenylphosphine (2.5 mL,15 mmol) was added to the system and the mixture was refluxed for 6h. After removal of the organic solvent by rotary evaporation, the remaining residue was extracted with dichloromethane (100 mL) and the organic phase was concentrated in vacuo to 10 mL and at 40 ℃ overnight to finally obtain phosphino in 86% yield (3.5 g) as a yellow-green powder.
Use of the above catalyst composition for ethylene trimerization: the components of the catalyst composition for ethylene trimerization are respectively dissolved in an inert solvent, and are sequentially injected or uniformly mixed in advance in a homogeneous catalyst mode to an ethylene trimerization reaction system, and then the ethylene pressure is increased to fully contact with the catalyst to carry out ethylene trimerization reaction to obtain the 1-hexene.
Further, the conditions for the ethylene trimerization reaction are as follows: the temperature is 30 to 250 ℃, the pressure is 0.5 to 20MPa, and the time is 0.1 to 2h; the inert solvent comprises benzene, toluene, cyclohexane, methylcyclohexane, n-heptane or n-hexane.
Further, the application of the catalyst composition for ethylene trimerization of the present invention in catalyzing ethylene trimerization reaction specifically comprises the following steps:
(1) Preparation of catalyst composition for ethylene trimerization: dissolving each component in the catalyst composition for ethylene trimerization in an inert solvent subjected to water removal treatment to prepare four solutions of a chromide, a pentaphenylphosphine pyrrole, an alkyl aluminum assistant and a depolymerizing agent for later use;
(2) Before reaction, firstly placing a reaction kettle body and a lining in an oven to dry overnight at 120 ℃, sealing after installing the reaction kettle on the reaction kettle, heating to 105 ℃ under a vacuum pumping condition, keeping the temperature for 1h, removing residual water, oxygen and oxygen-containing impurities, setting the temperature to be a reaction temperature, naturally cooling the reaction kettle, simultaneously filling nitrogen, then vacuumizing for three times, ensuring that air is completely replaced, then pumping away the nitrogen by using a vacuum pump, filling ethylene, and repeating for three times, and ensuring that the kettle body is filled with ethylene;
(3) Injecting the alkyl aluminum auxiliary solution prepared in the step (1) by using an injector under the condition of stirring, after the temperature is stabilized to the reaction temperature, sequentially injecting a chromide solution, a pentacenyl phosphino solution and a depolymerization reagent solution by using the injector, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording mass flow meter data, closing ethylene gas after the reaction is finished, stopping the reaction, closing an air inlet valve, detaching a reaction kettle body, and soaking the reaction kettle in an ice water bath to cool the reaction kettle to below 10 ℃.
After opening the vent valve to allow pressure to escape, a quantity of 5 ml of 10% HCl/ethanol solution was injected under stirring to quench the aluminum alkyl adjuvant, and the weight was weighed and recorded. A small amount of the liquid phase product was taken and analyzed by GC-MS. The remaining sample was filtered, the filter paper was weighed in advance to record the mass, then the polymer on the stirring paddle was scraped off with a spoon, washed into a beaker with a solvent, the resulting polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and calculated to obtain the mass of the polymer. The component types can be calibrated according to MS, and the selectivity and the catalyst activity of each product can be calculated according to GC results by combining the mass of the liquid phase product and the mass of the polymer.
Compared with the prior art, the invention has the following advantages:
conventional ethylene trimerization catalyst compositions are comprised of an organometallic salt, a ligand, an alkylaluminum cocatalyst, and a fourth component electron donor (halohydrocarbon). Wherein, the alkyl aluminum is unstable and extremely easy to polymerize during the use process and mainly exists in the form of dimer. The research suggests that 4 identical SPs are obtained after the nuclear electron hybridization of Al 3 Hybrid orbitals, in which three ethyl groups interact with Al, leaving a vacant SP 3 The orbitals are electron deficient and dimers are easily formed. On the other hand, the halogenated hydrocarbon can obviously improve the selectivity of the catalyst, and firstly, a halogen atom in the halogenated hydrocarbon can form a coordination bond with an Al atom in the alkyl aluminum, so that the alkyl aluminum of the dimer is disassembled into a monomolecular structure, and the concentration of an alkyl aluminum monomer is increased; and secondly, the halogen atom has larger electronegativity than the nitrogen atom and can open an N-H bond in the nitrogen-containing ligand, so that the nitrogen-containing ligand can exist in a catalytic system in a monomolecular mode and is beneficial to coordination with the central atom Cr. However, the halogenated hydrocarbon used at present is an organic halide, which has a serious environmental pollution although the activity and selectivity of the catalyst are greatly improved, and is a carcinogenic substance which has great harm to the bodies of operators.
Based on the above, under the condition that two main components of a chromium catalyst and an alkyl aluminum cocatalyst are not changed, inorganic phosphorus-containing halide is adopted as a depolymerizing agent for the first time, and pentaphenylphosphine pyrrole is used for replacing a pyrrole compound as a ligand, namely, the ethylene trimerization composition is composed of a chromium metal salt, a phosphino pyrrole compound, alkyl aluminum and an inorganic phosphorus-containing halide depolymerizing agent. The depolymerizing agent has proper electron-donating capability, can be combined with an alkyl aluminum reagent to prevent aggregation of the alkyl aluminum reagent, but does not influence the reducing capability of the alkyl aluminum reagent, and finally the catalyst composition has excellent ethylene trimerization catalytic performance. In addition, heteroatom phosphorus in a pyrrole ring in the pentaphenylphosphine has stronger electron donating performance, 5 benzene rings are connected, the whole system has moderate electron donating capability, the electron donating capability can be coordinated by two conjugated rings, the coordination with metal chromium, alkyl aluminum and inorganic phosphorus-containing halide electron donors can regulate the performance of a donor more flexibly, ethylene molecules and metals can be efficiently catalyzed to form a seven-membered ring, a 1-hexene molecule is released after beta dehydrogenation, and compared with the pyrrole compound, the pentaphenylphosphine compound has larger steric hindrance, can effectively reduce the generation of polymers, and is favorable for long-period reaction operation.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a pentaphenylphosphinolol prepared in example 1;
FIG. 2 shows the NMR phosphine spectrum of the pentaphenylphosphinole prepared in example 1.
Detailed Description
The present invention is further illustrated, but is not limited, by the following specific examples.
Example 1
The pentaphenylphosphinole compound was prepared by a dialkynyl reductive dimerization method, and when tolane and metallic lithium were reacted in the ratio of (1), the following reaction scheme occurred:
Figure DEST_PATH_IMAGE002
；
tolane (4.0 g,22 mmol) was dissolved in dry tetrahydrofuran (25 mL) and lithium turnings (140 mg,20 mmol) were added under argon. The reaction was stirred at room temperature overnight to give a dark green solution. Dichlorophenylphosphine (2.5 mL,15 mmol) was added to the system, and the mixture was refluxed for 6 hours. After removal of the organic solvent by rotary evaporation, the remaining residue was extracted with dichloromethane (100 mL) and the organic phase was concentrated in vacuo to 10 mL and at 40 ℃ overnight to finally obtain phosphino in 86% yield (3.5 g) as a yellow-green powder. 1H NMR (600 MHz, CDCl3): delta 7.44-7.42 (m, 2H), 7.24-7.21 (m, 2H), 7.08-7.01 (m, 16H), 6.99-6.97 (m, 4H). 31P NMR (162 MHz, CDCl3): δ 12.53 (PC 4). The pentacenyl phosphine pyrrole is subjected to purple nuclear magnetic resonance to characterize a hydrogen spectrum (figure 1 and figure 2), and the characteristic nuclear magnetic hydrogen spectrum and phosphine peak of the pentacenyl phosphine can prove the successful preparation of the compound.
Example 2
The ethylene oligomerization reaction is carried out in a high-pressure stainless steel reaction kettle. Before reaction, the high-pressure reaction kettle is heated to 100 ℃ under the condition of vacuum pumping and is kept at the constant temperature for 1h, then the temperature is set to 80 ℃, so that the high-pressure reaction kettle is naturally cooled, meanwhile, nitrogen is used for replacing for a plurality of times, and then ethylene is used for replacing for a plurality of times, so that the kettle body is ensured to be filled with ethylene. Subsequently, the solvent cyclohexane and the catalyst, in which the molar ratio of chromium acetylacetonate: pentaphenylphosphinole: triethyl aluminum: phosphorus trichloride = 1. Controlling the reaction pressure to be 4.5MPa, stopping the reaction after reacting for 1h, closing the air inlet valve, detaching the reaction kettle body, and soaking the reaction kettle body in ice-water bath to cool the reaction kettle to below 10 ℃. After opening the vent valve to allow pressure to escape, 5 mL of 10% HCl/ethanol solution was injected under stirring to quench the aluminum alkyl, which was then weighed and recorded. A small amount of the liquid phase product was taken and analyzed by GC-MS. The remaining sample was filtered, the filter paper weighed in advance to record the mass, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, the resulting polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and the mass of the polymer calculated. The component types can be calibrated according to MS, and the selectivity and the catalyst activity of each product can be calculated according to GC results and the combination of the mass of the liquid phase product and the mass of the polymer. The data results are shown in table 1.
Example 3
The same as example 1 except that the reaction temperature was 130 deg.C, the data results are shown in Table 1.
Example 4
The same as example 1 except that phosphorus trichloride was changed to phosphorus pentachloride, and the data results are shown in Table 1.
Example 5
The difference from example 1 is that phosphorus trichloride was changed to phosphorus tribromide, and the data results are shown in table 1.
Example 6
The same as example 1, except that phosphorus trichloride was changed to phosphorus pentabromide, and the data results are shown in Table 1.
Comparative example 1
The same as example 1 except that phosphorus trichloride was changed to hexachloroethane, and the data results are shown in Table 1.
Comparative example 2
The same as example 1, except that pentaphenylphosphine was changed to pyrrole, the data results are shown in Table 1.
Comparative example 3
The difference from comparative example 2 is that phosphorus trichloride was changed to hexachloroethane and pentaphenylphosphine pyrrole was changed to pyrrole, and the data results are shown in Table 1.
TABLE 1 summary of the reaction conditions and the reaction Performance for the examples of the invention and the comparative examples
Figure 39556DEST_PATH_IMAGE003
The above examples are merely for clearly illustrating the present invention and the embodiments of the present invention are not limited thereto. Any modification, replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (8)

1. A catalyst composition for the trimerization of ethylene characterized in that: comprises the following components:
(1) Chromium compound: chromium isooctanoate, chromium acetylacetonate or chromium tetrahydrofuran chloride;
(2) Ligand: pentaphenylphosphinolol of the formula:
Figure 912396DEST_PATH_IMAGE001
；
(3) An alkyl aluminum additive: triethylaluminum, methylaluminoxane, trimethylaluminum or isobutylaluminum;
(4) Depolymerizing agent: PCl 3 、PCl 5 、PBr 5 Or PBr 3 。
2. Catalyst composition for the trimerization of ethylene according to claim 1, characterized in that: the preparation method of the pentaphenyl phosphinyl comprises the following steps: dissolving tolane in tetrahydrofuran, adding lithium scrap under the protection of argon, stirring the reaction at room temperature overnight to obtain a dark green solution, adding dichlorophenyl phosphine, refluxing the mixture for 6h, removing an organic solvent through rotary evaporation, extracting dichloromethane, concentrating an organic phase in vacuum, and standing overnight at 40 ℃ to obtain yellow green powdery phosphinothricin, namely pentaphenyl phosphinothricin.
3. Catalyst composition for the trimerization of ethylene according to claim 1, characterized in that: the mole ratio of the chromide to the pentaphenylphosphine pyrrole to the alkyl aluminum additive to the depolymerizing agent is as follows: 1, 0.1 to 100, 1 to 1000.
4. Catalyst composition for the trimerization of ethylene according to claim 3, characterized in that: the molar ratio of the chromide to the pentacenyl phosphino to the alkyl aluminum additive to the electron donor is 1.1 to 10.
5. Catalyst composition for the trimerization of ethylene according to claim 4, characterized in that: the molar ratio of the chromide to the pentaphenylpyrrole to the alkyl aluminum additive to the depolymerizing agent is 1:1 to 8:1 to 100 parts by weight.
6. Use of a catalyst composition for the trimerization of ethylene according to any of the claims 1-5, characterized in that: the components of the catalyst composition for ethylene trimerization are respectively dissolved in an inert solvent, and are sequentially injected or uniformly mixed in advance in a homogeneous catalyst mode to an ethylene trimerization reaction system, and then the ethylene pressure is increased to fully contact with the catalyst to carry out ethylene trimerization reaction to obtain the 1-hexene.
7. Use according to claim 6, characterized in that: the conditions for the ethylene trimerization reaction are as follows: the temperature is 30 to 250 ℃, the pressure is 0.5 to 20MPa, and the time is 0.1 to 2h.
8. Use according to claim 7, characterized in that: the inert solvent comprises benzene, toluene, cyclohexane, methylcyclohexane, n-heptane or n-hexane.
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