CN115028509A - Ethylene oligomerization process with increased reactivity and reduced polymer formation - Google Patents

Ethylene oligomerization process with increased reactivity and reduced polymer formation Download PDF

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CN115028509A
CN115028509A CN202210779080.XA CN202210779080A CN115028509A CN 115028509 A CN115028509 A CN 115028509A CN 202210779080 A CN202210779080 A CN 202210779080A CN 115028509 A CN115028509 A CN 115028509A
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chromium
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pnp
pentafluorophenyl
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CN115028509B (en
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丁明强
张彦雨
陈冠良
车传亮
王大林
王磊
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Wanhua Chemical Group Co Ltd
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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
    • 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
    • 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
    • B01J31/18—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
    • B01J31/189—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 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • 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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Abstract

The invention relates to a control process for ethylene oligomerization, in particular to a method for maintaining activity and byproduct polymer in a control range on the premise of limiting impurity types and contents. The oligomerization process with ideal activity and byproduct polymer content is realized mainly by limiting the amount of hydroxyl and/or amino compounds in the system within a specific range and under the condition of not changing the main formula and process of oligomerization reaction.

Description

Ethylene oligomerization process with increased reactivity and reduced polymer formation
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a method for reducing a byproduct PE (polyethylene) in an ethylene oligomerization reaction on the basis of not sacrificing product selectivity and polymerization activity.
Background
The linear alpha-olefin has wide industrial application, and the oligomer can be used in the fields of plasticizers, fatty acids, lubricating oil additives and the like; the copolymer can be used for producing polyolefin elastomers and can be used in the fields of shoe materials, polymer modification, automobiles and the like.
Since the Sasol company in 2003 adopts a chromium compound with a nitrogen-phosphorus coordination framework as a catalyst to catalyze ethylene tetramerization at 45 ℃ and 4.5MPa to generate 16.6-32.7% of 1-hexene and 44-67% of 1-octene, research on the aspects is not earnestly made at home and abroad, and the research is mostly focused on structural design of a catalyst ligand and optimization of reaction equipment/process. Due to the special property of the chromium catalyst, the ethylene tetramerization inevitably generates partial polymers, and the long-time accumulation of the polymers causes blockage of a reaction kettle, a stirrer, a valve and a pipeline and influences heat transfer and mass transfer; moreover, the reaction uses a large amount of alkyl aluminum compound as a cocatalyst, the source is limited and the price is high, and how to reduce the dosage and improve the reaction activity is very necessary for reducing the production cost.
The patent (grant publication No. CN104271537B) reports that an oligomerization process of ethylene with reduced polymer formation can achieve better effects by specifically introducing a non-metal oxygen-containing additive into a reaction system to improve the reaction activity and reduce the generation of polymers, and preferably gaseous oxygen-containing additives. However, the content of gaseous impurities is difficult to control and affects the purity of the product, so that the development of a simpler and more efficient ethylene oligomerization process for increasing the reaction activity and reducing the polymer content is needed.
Disclosure of Invention
The invention aims to provide a method for improving the ethylene oligomerization reaction activity, which can increase the reaction activity on the basis of not sacrificing the product selectivity and by-product PE.
Although hydroxyl and amine compounds are generally considered as poisoning agents for the oligomerization of ethylene, even more so, the reaction may be terminated. However, the inventors have surprisingly found that in the existing catalytic system, by controlling the amount of the hydroxyl or amine compound in the system within a specific range, an oligomerization process having both high reactivity and low content of by-product polymer can be realized without changing the main formula and process of the oligomerization reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
ethylene oligomerization methodCharacterized in that the process is carried out at a reaction temperature and pressure such that ethylene is oligomerized to form an alpha-olefin in a system comprising a chromium salt/PNP ligand, an alkyl aluminum compound, a boron salt and an organic solvent, wherein the content of hydroxyl compound and/or amine compound in the system relative to the amount of organic solvent satisfies the following relationship: m is less than or equal to 0.4ppm (OH) +m (NH2) ≤4ppm。
In the invention, the reaction temperature is 45-50 ℃, and the reaction pressure is 4.0-5.0 MPaG.
In the present invention, the alkyl aluminum compound is selected from one or more of triethylaluminum, triisobutylaluminum, trioctylaluminum, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO).
In the invention, the chromium-containing salt is a complex of metallic chromium, and is specifically selected from one or more of tetrahydrofuran chromium trichloride, chromium acetylacetonate, chromium 2-ethylhexanoate and chromium hexacarbonyl.
In the invention, the PNP ligand is a compound with a phosphine nitrogen structure as a framework, and is selected from one or more of N, N-bis (diphenylphosphino) -isopropylamine (iPr-PNP), N-bis (diphenylphosphino) -tert-butylamine (tBu-PNP), N-bis (diphenylphosphino) -1, 2-dimethylpropylamine (1,2-DMP-PNP) and N, N-bis (diphenylphosphino) -cyclohexylamine (Cy-PNP).
In the present invention, the boron salt is a boron-containing organic compound selected from one or more of tris (pentafluorophenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate-methyldi- (hexadecyl) ammonium tetrakis (pentafluorophenyl) borate, and tetrakis (pentafluorophenyl) borate-methyldi- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate.
In the present invention, the molar ratio of the chromium-containing salt to the PNP ligand is 0.5 to 5, preferably 1 to 2.
In the present invention, the molar ratio of the alkyl aluminum compound to the chromium-containing salt is 10 to 1000, preferably 200-500.
In the present invention, the molar ratio of the boron salt to the chromium-containing salt is 0.5 to 3, preferably 1 to 2.
In the present invention, the mass ratio of the hydroxyl and amine-based compound to the aluminum alkyl (oxy) group is 0.05 to 5:100, preferably 0.3 to 3: 100.
In the present invention, the organic solvent is selected from one or more of n-hexane, n-heptane, cyclohexane, methylcyclohexane, tetrahydrofuran, toluene, or xylene.
In the present invention, the hydroxyl/amine group-containing compound is derived from ethylene or solvent entrainment or deliberate introduction: the hydroxyl compound is selected from one or more of deionized water, 1-hexanol, 1-octanol, 1-decanol or 2-ethyl-hexanol; the amino compound is one or more of tert-butylamine, 1-hexylamine, 1-octylamine, 1-decylamine, dodecylamine or 2-ethyl-hexylamine.
In the invention, the selectivity of 1-hexene and 1-octene in the alpha-olefin reaches 90-92%, the reaction activity reaches more than 800Kg/g Cr, and the polymer content is less than 0.3%.
Compared with the prior art, the invention has the beneficial effects that:
(1) on one hand, the invention simplifies the purification process of the solvent or the raw material, so that the raw material reacts under the condition of containing a certain amount of polar compounds, such as hydroxyl or amido, thereby simplifying the operation difficulty, improving the efficiency and reducing the operation cost.
(2) On the other hand, in the presence of hydroxyl or amino compounds, the catalyst and the alkyl aluminum compound in the system can perform certain on-line hydrolysis reaction to generate partial other types of cocatalysts in situ, so that the using amount of alkyl aluminum is reduced, or more other types of active centers are formed, the reaction activity is improved, and the raw material cost is reduced.
Detailed Description
The following examples are provided to further illustrate the technical solutions provided by the present invention, but the present invention is not limited to the listed examples, and also includes any other known modifications within the scope of the claims of the present invention.
The raw material information related to the invention is as follows:
TABLE 1 Source of raw materials and their specifications
Figure BDA0003725164870000041
Figure BDA0003725164870000051
Secondly, the test method of the sample in the invention is as follows:
the liquid phase products are characterized by gas chromatography, so that the mass of each liquid phase product is obtained, and the solid products are separated, dried and weighed;
analysis conditions for gas chromatography: the temperature of the sample injection is 250 ℃; the temperature of the column box is 35 ℃;
temperature rising procedure: firstly keeping the temperature at 35 ℃ for 10 minutes, then increasing the temperature to 250 ℃ at a speed of 10 ℃/min, then keeping the temperature at 250 ℃ for 10 minutes, and then beginning to cool until the temperature reaches the room temperature;
detector temperature: 250 ℃; carrier: 1.0 Mpa; air: 0.03 MPa; hydrogen gas: 0.03 MPa;
the characterization of the product is carried out by taking n-nonane as an internal standard substance and the calculation method is as follows:
Figure BDA0003725164870000052
in the formula, m1 represents the mass of a certain substance, m is the mass of nonane, a1 is the peak area of the substance measured in a GC, and a is the peak area of n-nonane measured in a GC. k is a correction coefficient.
Example 1
A500 mL high pressure stainless steel autoclave was heated to 120 deg.C, evacuated for 3h during which time nitrogen was replaced three times, then evacuated and replaced three times with hydrogen. After the temperature was cooled to room temperature, hydrogen gas was introduced under a pressure of 0.5MPa, and 195mL of dehydrated and deoxidized methylcyclohexane (containing 0.4ppm of 2-ethyl-1-hexanol), 0.4mL of Modified Methylaluminoxane (MMAO), 2mL of a previously prepared solution of a phosphine ligand (N, N-bis (diphenylphosphino) -tert-butylamine/chromium salt (chromium acetylacetonate) catalyst having a molar concentration of 1.0umol/L, and 2mL of a previously prepared methylcyclohexane solution of tetrakis (pentafluorophenyl) borate-methyldi- (octadecyl) ammonium salt having a molar concentration of 1.0umol/L were added thereto, and the ethylene pressure was maintained at 4.5MPa, and the reaction was carried out at a reaction temperature of 48 ℃ and a rotation speed of 600rpm for 45 minutes.
After the reaction is finished, the reaction solution is filtered, the supernatant is subjected to GC analysis, and the solid product is dried in a vacuum oven at the temperature of 80 ℃ for 12 hours and weighed, so that the activity and the selectivity of the product are calculated.
Example 2
The remaining operation of example 1 was repeated except that the amount of 2-ethyl-1-hexanol added was changed to 1 ppm.
Example 3
The remaining operation of example 1 was repeated except that the amount of 2-ethyl-1-hexanol added was changed to 2 ppm.
Example 4
The remaining operation of example 1 was repeated except that the amount of 2-ethyl-1-hexanol added was changed to 4 ppm.
Example 5
A500 mL high pressure stainless steel autoclave was heated to 120 deg.C, evacuated for 3h during which time nitrogen was replaced three times, then evacuated and replaced three times with hydrogen. After the temperature is cooled to room temperature, hydrogen is introduced under 0.5MPa, 197mL of dehydrated and deoxidized methylcyclohexane (containing 1.5ppm of 1-decanol), 0.24mL of Modified Methylaluminoxane (MMAO), 2mL of a previously prepared phosphine ligand (N, N-bis (diphenylphosphino) -1, 2-dimethylpropylamine/chromium salt (chromium acetylacetonate) catalyst solution with a molar concentration of 0.5umol/L, and 1mL of a previously prepared methylcyclohexane solution of tetrakis (pentafluorophenyl) borate-methyldi- (hexadecyl) ammonium salt with a molar concentration of 1.0umol/L are added thereto, and the ethylene pressure is maintained at 4.5MPa, and the reaction is carried out at 45 ℃ and 600rpm for 30 min.
Example 6
A500 mL high pressure stainless steel autoclave was heated to 120 deg.C, evacuated for 3h during which time nitrogen was replaced three times, then evacuated and replaced three times with hydrogen. After the temperature is cooled to room temperature, hydrogen is introduced under 0.5MPa, 195mL of dehydrated and deoxidized methylcyclohexane solution (containing 1ppm of deionized water), 0.3mL of Triethylaluminum (TEA), 2mL of a previously prepared phosphine ligand (N, N-bis (diphenylphosphino) -isopropylamine/chromate (tetrahydrofuran chromium trichloride) catalyst solution with a molar concentration of 0.3umol/L, and 2mL of a previously prepared toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate with a molar concentration of 0.3umol/L are added thereto, the ethylene pressure is maintained at 4.5MPa, and the reaction is carried out at 48 ℃ and 600rpm for 60 min.
Example 7
A500 mL high pressure stainless steel autoclave was heated to 120 deg.C, evacuated for 3h during which time nitrogen was replaced three times, then evacuated and replaced three times with hydrogen. After the temperature was cooled to room temperature, hydrogen gas was introduced under a pressure of 0.5MPa, and 193mL of a dehydrated and deoxidized methylcyclohexane solution (containing 4ppm of dodecylamine), 0.9mL of Triisobutylaluminum (TIBA), 3mL of a previously prepared phosphine ligand (N, N-bis (diphenylphosphino) -cyclohexylamine/chromate (tetrahydrofuran chromium trichloride) catalyst solution having a molar concentration of 1.0. mu. mol/L, and 3mL of a previously prepared toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate having a molar concentration of 1.0. mu. mol/L were added thereto, and the ethylene pressure was maintained at 4.5MPa, and the reaction was carried out at a reaction temperature of 48 ℃ and a rotation speed of 600rpm for 30 minutes.
Comparative example 1
The remaining operation of example 1 was repeated except that the amount of 2-ethyl-1-hexanol added was changed to 0 ppm.
Comparative example 2
The remaining operation of example 1 was repeated except that the amount of 2-ethyl-1-hexanol added was changed to 6 ppm.
Comparative example 3
The remaining operation of example 1 was repeated except that the amount of 2-ethyl-1-hexanol added was changed to 8 ppm.
The composition of the oligomerization reaction obtained by the methods described above is shown in the following table:
example of operation External additive Addition amount/ppm reactivity/Kg/g Cr 1-C6/％ 1-C8/％ PE/％
Example 1 2-ethyl-1-hexanol 0.4 800 43.7％ 47.9％ 0.3
Example 2 2-ethyl-1-hexanol 1 900 43.3％ 47.5％ 0.2
Example 3 2-ethyl-1-hexanol 2 880 43.2％ 47.8％ 0.2
Example 4 2-ethyl-1-hexanol 4 830 43.0％ 47.3％ 0.2
Example 5 1-decanol 1.5 870 32.3％ 57.7％ 0.3
Example 6 H 2 O 1 960 25.7％ 65.6％ 0.2
Example 7 Dodecyl amine 4 850 40.5％ 50.3％ 0.2
Comparative example 1 Is free of 0 680 44.2％ 47.3％ 0.5
Comparative example 2 2-ethyl-1-hexanol 6 500 43.1％ 45.7％ 1.7
Comparative example 3 2-ethyl-1-hexanol 8 100 42.8％ 45.4％ 2.8
From the examples and comparative examples, it can be seen that: a certain amount of compound containing hydroxyl or amino is added in the oligomer system, so that the polymerization reaction activity is improved and the generation of a byproduct polymer PE is reduced under the condition of keeping the selectivity basically unchanged. Without these additives in the system, the activity was slightly lower and the PE was more abundant; if the additive in the system is excessive, the additive can play a role of a quenching agent, and the activity is reduced or even the activity is inactivated.
In conclusion, the above description is only a representative embodiment of the present invention and is intended to illustrate the present invention, not to limit the present invention, and any modifications of the present invention, including equivalent replacement and addition of raw materials, conversion of continuous or batch processes, etc., are within the scope of the present invention, which should be understood by those skilled in the art. The scope of the invention is defined by the appended claims.

Claims (10)

1. A process for oligomerization of ethylene, characterized in that ethylene is oligomerized at a reaction temperature and pressure in a system comprising a chromium salt/PNP ligand, an alkylaluminum compound, a boron salt and an organic solvent to form an alpha-olefin, wherein the content of hydroxyl compounds and/or amine compounds in the system relative to the amount of organic solvent satisfies the following relationship: m is less than or equal to 0.4ppm (OH) +m (NH2) ≤4ppm。
2. The process of claim 1, wherein the reaction temperature is 45 to 50 ℃ and the reaction pressure is 4.0 to 5.0 MPaG.
3. The process of claim 1 or 2, wherein the alk (oxy) yl aluminum compound is selected from one or more of triethylaluminum, triisobutylaluminum, trioctylaluminum, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO).
4. A process according to any one of claims 1 to 3, wherein the chromium-containing salt is a complex of metallic chromium, in particular selected from one or more of chromium trichloride tetrahydrofuran, chromium acetylacetonate, chromium 2-ethylhexanoate and chromium hexacarbonyl.
5. The method of any one of claims 1-4, wherein the PNP ligand is a compound having a phosphinothricin structure as a backbone and is selected from one or more of N, N-bis (diphenylphosphino) -isopropylamine (iPr-PNP), N-bis (diphenylphosphino) -tert-butylamine (tBu-PNP), N-bis (diphenylphosphino) -1, 2-dimethylpropylamine (1,2-DMP-PNP), N-bis (diphenylphosphino) -cyclohexylamine (Cy-PNP).
6. The method of any one of claims 1-5, wherein the boron salt is a boron-containing organic compound selected from one or more of tris (pentafluorophenyl) boron, triphenylcarbetetrakis (pentafluorophenyl) borate, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, methyldi- (hexadecyl) ammoniumtetrakis (pentafluorophenyl) borate, and methyldi- (octadecyl) ammoniumtetrakis (pentafluorophenyl) borate.
7. The method according to any one of claims 1 to 6, wherein the mass ratio of the mass of the hydroxyl and amine based compound to the mass of the alk (oxy) yl aluminium is between 0.05 and 5:100, preferably between 0.3 and 3: 100.
8. The process according to any one of claims 1 to 7, wherein the molar ratio of chromium-containing salt to PNP ligand is from 0.5 to 5, preferably from 1 to 2; and/or the molar ratio of the alkyl aluminum compound to the chromium-containing salt is 10 to 1000, preferably 200-500; and/or the molar ratio of the boron salt to the chromium-containing salt is 0.5 to 3, preferably 1 to 2.
9. The method of any one of claims 1-8, wherein the organic solvent is selected from one or more of n-hexane, n-heptane, cyclohexane, methylcyclohexane, tetrahydrofuran, toluene, or xylene.
10. The method of any one of claims 1 to 9, wherein the hydroxyl compound is selected from one or more of deionized water, 1-hexanol, 1-octanol, 1-decanol, or 2-ethyl-hexanol; the amino compound is one or more of tert-butylamine, 1-hexylamine, 1-octylamine, 1-decylamine, dodecylamine or 2-ethyl-hexylamine.
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