CN109201118B - Supported ethylene oligomerization catalyst, and preparation method and application thereof - Google Patents

Supported ethylene oligomerization catalyst, and preparation method and application thereof Download PDF

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CN109201118B
CN109201118B CN201710546543.7A CN201710546543A CN109201118B CN 109201118 B CN109201118 B CN 109201118B CN 201710546543 A CN201710546543 A CN 201710546543A CN 109201118 B CN109201118 B CN 109201118B
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catalyst
oligomerization
ethylene
carbon nano
nano tube
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CN109201118A (en
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宗明生
荣峻峰
谢婧新
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • C07C2/22—Metal halides; Complexes thereof with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium
    • 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

Abstract

The invention relates to a supported ethylene oligomerization catalyst, wherein, the carrier is a carbon nano tube, and an active component is supported in the carbon nano tube; wherein the active component is formed by ZrX4With C3-C8 alkanol. The catalyst of the present invention can improve the product distribution of the oligomerization product and increase the yield of alpha-olefin.

Description

Supported ethylene oligomerization catalyst, and preparation method and application thereof
Technical Field
The invention relates to a supported ethylene oligomerization catalyst, a preparation method and application thereof, in particular to an ethylene oligomerization catalyst taking carbon nano tubes as a carrier, and a preparation method and application thereof.
Background
It is customary in industry to refer to terminal olefins of C4 or greater (double bonds at the ends of the molecular chain) as alpha-olefins. Alpha-olefins, which are industrial products, have a wide distribution of carbon numbers (C4-C40), and are widely used as linear alpha-olefins having carbon numbers in the range of C6-C20.
The olefin oligomerization is a main way for producing alpha-olefin, the current mature processes include a Gulf method, an Ethyl method and an SHOP method, catalysts used in the three processes are alkyl aluminum or nickel compounds, the reaction conditions are severe, and the pressure can reach dozens of MPa generally. Compared with the three processes, when the zirconium compound is used as the catalyst, the reaction conditions are relatively mild, the pressure is generally between 2MPa and 3MPa, but the low-carbon part in the oligomerization product is more.
CN101745422A discloses an olefin oligomerization catalyst, a preparation method and an application thereof, wherein the catalyst is alkoxy zirconium chloride, and the obtained oligomerization product contains less low carbon part but more C20 +. CN101816951A discloses an ethylene oligomerization catalyst and a preparation method thereof, which reduces the content of C20+ in oligomerization products to a certain extent by carrying out silicon modification on zirconium oxychloride. Although the foregoing documents have made improvements to zirconium-based ethylene oligomerization catalysts, there is still room for improvement in the yields of fractions C6 to C20 and in the yields of alpha-olefins.
In addition, zirconium-based ethylene oligomerization catalysts generally lead to the formation of high polymers, which block the lines during the oligomerization process and seriously impair the industrial production, and the aforementioned documents do not mention this.
Carbon Nanotubes (CNTs), which were discovered in 1991, are tubes composed of a hexagonal lattice like graphite, which may be composed of single or multiple layers. The fields in which carbon nanotubes have been used as catalyst carriers are: methanol synthesis and decomposition, catalytic oxidation, ammonia synthesis, fischer-tropsch synthesis, dehydrogenation, and fuel cells. No report of using carbon nanotube as ethylene oligomerization catalyst carrier is found.
Disclosure of Invention
The invention provides a supported ethylene oligomerization catalyst, a preparation method and application thereof, the catalyst can improve the product distribution of oligomerization products and improve the yield of alpha-olefin; the polymerization under specific conditions can also avoid the generation of high polymers.
The present invention mainly includes the following matters.
1. A load type ethylene oligomerization catalyst is characterized in that a carrier is a carbon nano tube, and an active component is loaded in the carbon nano tube; wherein the active component is formed by ZrX4With C3-C8 alkanol.
2. The catalyst according to 1, characterized in that in the reaction for preparing the active component, an alkanol is reacted with ZrX4The molar ratio of (a) to (b) is 3:1 to 9:1, preferably 3:1 to 6: 1.
3. The catalyst according to any of the preceding claims, characterized in that the tube diameter of the carbon nanotubes is between 5nm and 30nm, preferably between 8nm and 25nm, more preferably between 8nm and 15 nm.
4. The catalyst according to any of the preceding claims, characterized in that the Zr content is 0.5% to 20%, preferably 1% to 15%, more preferably 1% to 5% based on the mass of the catalyst.
5. A catalyst according to any one of the preceding claims, characterized in that the alkanol is n-butanol.
6. Load type BThe preparation method of the alkene oligomerization catalyst is characterized by comprising the following steps: (1) in an inert solvent, ZrX4Reacting with C3-C8 alkanol to obtain a solution; (2) and (3) fully contacting the solution prepared in the step (1) with the roasted carbon nano tube.
7. The method according to 6, wherein the carbon nanotubes have a tube diameter of 5nm to 30nm, preferably 8nm to 25nm, and more preferably 8nm to 15 nm.
8. The method according to 6 or 7, characterized in that the baking temperature of the carbon nanotubes is 800 ℃ to 1800 ℃; preferably 1000 ℃ to 1400 ℃; the roasting time is 1-10 h, preferably 2-8 h.
9. The method according to any one of claims 6 to 8, wherein the carbon nanotubes are pretreated before being calcined, and the pretreatment method comprises: placing the carbon nano tube in mixed acid of sulfuric acid and nitric acid, and treating for 1-10 h, preferably treating for 2-8 h at normal temperature; the mass concentration of the sulfuric acid is more than 95%, the mass concentration of the nitric acid is more than 60%, and the volume ratio of the sulfuric acid to the nitric acid is 0.5: 1-5: 1, preferably 1: 1-4: 1, and more preferably 2.5: 1-3.5: 1.
10. The method according to any one of claims 6 to 9, wherein the inert solvent is benzene, toluene or xylene.
11. A supported ethylene oligomerization catalyst is characterized by being prepared by any one of 6-10 methods.
12. A process for oligomerization of ethylene to linear alpha-olefins, characterized in that ethylene is oligomerized to linear alpha-olefins in an inert solvent in the presence of a supported catalyst as described in 1 or 11 and an alkylaluminum cocatalyst.
13. The method according to 12, wherein the molar ratio of aluminum to zirconium is 1:1 to 200:1, preferably 5:1 to 150: 1; the oligomerization temperature is 20-200 ℃, preferably 60-150 ℃; the ethylene pressure is 0.1MPa to 20 MPa.
14. The process according to 12 or 13, characterized in that the ethylene pressure is from 8MPa to 20 MPa.
15. The method according to any one of 12 to 14, characterized in that the alkylaluminum cocatalyst is one or more of triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, monoethylaluminum dichloride, triethylaluminum trichloride and trimethylaluminum trichloride.
Compared with the prior art, the oligomerization product is more reasonably distributed, the yield of the alpha-olefin is higher, and the generation of high polymer can be avoided.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a transmission electron micrograph of carbon nanotubes before and after loading in example 1.
FIG. 2 is a transmission electron micrograph of carbon nanotubes before and after loading in example 2.
FIG. 3 is a transmission electron micrograph of carbon nanotubes before and after loading in example 3.
Fig. 4 is a transmission electron micrograph of the carbon nanotubes before and after loading in comparative example 1.
Detailed Description
Technical terms in the present invention are defined according to the definitions given herein, and terms not defined are understood according to the ordinary meanings in the art.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The numerical points disclosed in the specification include not only the numerical points specifically disclosed but also the endpoints of each numerical range, and any combination of these numerical points should be considered as the range disclosed or described in the present invention, regardless of whether the numerical pairs are disclosed herein.
The invention provides a load type ethylene oligomerization catalyst, wherein the carrier of the catalyst is a carbon nano tube, and an active component is loaded in the carbon nano tube; wherein the active component is formed by ZrX4With C3-C8 alkanol.
According to the invention, said ZrX4Zirconium tetrachloride is preferred.
According to the invention, for ZrX4The reaction with the alkanol is not particularly restricted and the person skilled in the art can select suitable means known in the art.
According to the invention, in the reaction for preparing the active component, an alkanol is reacted with ZrX4The molar ratio of (a) to (b) is 3:1 to 9:1, preferably 3:1 to 6: 1.
According to the invention, the tube diameter of the carbon nano tube is 5nm to 30nm, preferably 8nm to 25nm, and more preferably 8nm to 15 nm.
According to the present invention, the Zr content is 0.5% to 20%, preferably 1% to 15%, more preferably 1% to 5%, based on the mass of the catalyst.
According to the invention, the alkanol is n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, isohexanol or isooctanol.
The invention provides a preparation method of a supported ethylene oligomerization catalyst, which comprises the following steps: (1) in an inert solvent, ZrX4Reacting with C3-C8 alkanol to obtain a solution; (2) and (3) fully contacting the solution prepared in the step (1) with the roasted carbon nano tube.
In the invention, the inert solvent is a solvent which is harmless to the catalytic performance of the ethylene oligomerization catalyst and the ethylene oligomerization reaction.
According to the present invention, in the step (1), the inert solvent is preferably benzene, toluene, xylene, trimethylbenzene, n-hexane or cyclohexane, and any mixture thereof.
In the preparation method, the raw materials and the ratio thereof are the same as the corresponding contents in the catalyst part, and the invention is not repeated herein.
Preferably, in step (1), zirconium tetrachloride is added to toluene, then alkanol is added, and the reaction is stirred at 60 ℃ to 80 ℃ until the zirconium tetrachloride is completely dissolved to form a homogeneous solution.
According to the invention, the tube diameter of the carbon nano tube is 5nm to 30nm, preferably 8nm to 25nm, and more preferably 8nm to 15 nm.
According to the invention, the roasting temperature of the carbon nano tube is 800-1800 ℃; preferably 1000 ℃ to 1400 ℃; the roasting time is 1-10 h, preferably 2-8 h. It is known in the art that the baking of carbon nanotubes needs to be performed under the protection of an inert atmosphere (e.g., nitrogen).
According to the present invention, the contacting temperature in step (2) may be carried out at normal temperature to a higher temperature (e.g., 200 ℃), preferably at normal temperature to 50 ℃, and more preferably at normal temperature.
The carbon nanotubes need to be pretreated before use, and the method to be treated can be performed with reference to the existing literature or the instructions for use of commercially available products. For example, the following pretreatment methods are adopted: placing the carbon nano tube in mixed acid of sulfuric acid and nitric acid, treating for 1-10 h, preferably treating for 2-8 h at normal temperature, and then washing, separating and drying to obtain a pretreated carbon nano tube; wherein the mass concentration of the sulfuric acid is more than 95% (for example, the mass concentration is 98%), the mass concentration of the nitric acid is more than 60% (for example, the mass concentration is 65%), and the volume ratio of the sulfuric acid to the nitric acid is 0.5: 1-5: 1, preferably 1: 1-4: 1, and more preferably 2.5: 1-3.5: 1. According to the present invention, an ultrasonic device may be additionally used in the pretreatment step to improve the efficiency of pretreatment.
According to the invention, the inert solvent is preferably benzene, toluene, xylene, trimethylbenzene, n-hexane or cyclohexane, and any mixtures thereof.
According to the invention, the solid in the step (2) is separated and dried to obtain the supported ethylene oligomerization catalyst.
The invention also provides a supported ethylene oligomerization catalyst, which is prepared by any one of the methods of 6-9.
The invention also provides an ethylene oligomerization method for preparing linear alpha-olefin, which comprises the following steps: in an inert solvent, in the presence of the supported catalyst and an aluminum alkyl cocatalyst, oligomerizing ethylene to linear alpha-olefins.
The aluminum alkyl cocatalysts are known in the art. Typically, the aluminum alkyl cocatalyst is of the formula AlRnX3-nAnd (c) a compound, wherein n is 1 to 3. The alkyl aluminum cocatalyst is preferably one or more of triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, triethyl aluminum trichloride and trimethyl aluminum trichloride.
According to the invention, the molar ratio of aluminum to zirconium is 1:1 to 200:1, preferably 5:1 to 150: 1; the oligomerization temperature is 20-200 ℃, preferably 60-150 ℃.
According to the invention, the ethylene oligomerization method for preparing linear alpha-olefin can be implemented in a wider ethylene pressure range, such as 0.1MPa to 20 MPa. The oligomerization pressure of the existing zirconium catalyst is generally between 2MPa and 3MPa, and the method can be implemented in the range, so that a better oligomerization effect is obtained. However, the process of the invention is carried out at higher ethylene pressures, for example from 8MPa to 20MPa, and the formation of high polymers can be avoided. In the invention, the preferable ethylene oligomerization pressure is 8MPa to 12 MPa.
The invention can selectively fill the zirconium active component in the carbon nano tube, so that the ethylene oligomerization reaction has the characteristics of high reaction activity, high alpha-olefin yield and the like.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the examples and comparative examples, the difference in mass of the oligomerization system before and after the reaction was the mass of the reaction product, and the catalyst activity was calculated from this mass.
In the examples and comparative examples, the liquid product and the solid product were separated by filtration. Adding 0.5M sodium hydroxide-ethanol solution into the liquid product to terminate the reaction, washing with water, and performing gas chromatography quantitative analysis on the liquid product distribution (gas chromatograph is Agilent 7890A, SE-52 type chromatographic column, temperature-rising program of the chromatogram is that the initial temperature is 45 deg.C, staying for 4 min, then rising to 270 deg.C at 25 deg.C/min, gasifying, and detecting temperature is 300 deg.C). The solid product was washed with ethanol, placed in an evaporation dish, dried and weighed.
In the examples and comparative examples, the liquid product distribution was calculated as the mass fraction of each liquid product component on the basis of the mass of the liquid product.
The calculation formulas for the polymer content and the α -olefin yield in table 1 are respectively:
the polymer content (mass of solid product/mass of reaction product) x 100%
α -olefin yield ═ mass of α -olefin/mass of liquid product x 100%
In the examples and comparative examples, the internal structure and morphology of the catalyst were observed by using an H-800 Transmission Electron Microscope (TEM) (product of Hitachi, Japan). The technical standard is as follows: the acceleration voltage was 200 kV.
In the examples and comparative examples, the zirconium content of the catalysts was measured by Rigaku 3013 type X-ray fluorescence photometer.
Example 1
This example serves to illustrate the preparation of the supported catalyst of the present invention.
(1) Preparation of the active ingredient
10mmol of zirconium tetrachloride was suspended in 34.6 g of toluene, stirred at 70 ℃ for 1 hour, and then 30mmol of n-butanol was added thereto, and the reaction was refluxed at 85 ℃ for 4 hours to obtain a solution. The temperature of the system after the reaction is reduced to 25 ℃, and 20 g of toluene is added to prepare a toluene solution with the zirconium concentration of 0.2 mol/L.
(2) Preparation of Supported catalysts
(a) Putting 10g of carbon nanotubes (the pipe diameter is 8-15 nm) into 360ml of mixed acid of concentrated sulfuric acid (98 m%) and 140ml of concentrated nitric acid (65 m%), carrying out ultrasonic treatment by using an ultrasonic instrument for 7 hours, washing, separating and drying. Then, the carbon nano tube is roasted under the protection of nitrogen, the roasting temperature is 1200 ℃, and the roasting time is 5 hours, so that oxygen-containing groups and amorphous carbon in the carbon nano tube are removed, and the treated carbon nano tube is obtained;
(b) and (3) adding 0.5g of the carbon nano tube treated in the step (2) into 5ml of the solution prepared in the step (1), stirring for 5 hours at normal temperature, and then performing nitrogen purging until the supported catalyst is completely dried to obtain the supported catalyst A.
The zirconium content of catalyst A was found to be 1.81%.
(a) The electron micrograph of the carbon nanotube after the treatment in (b) and the electron micrograph of the catalyst-supported carbon nanotube in (b) are shown in fig. 1.
Example 2
This example serves to illustrate the preparation of the supported catalyst of the present invention.
The active component and the supported catalyst were prepared as in example 1, except that: (a) the roasting temperature in the process is 1000 ℃, and the roasting time is 8 hours. To prepare the supported catalyst B.
The zirconium content of catalyst B was found to be 1.78%.
(a) An electron micrograph of the carbon nanotube after the treatment in (b) and an electron micrograph of the catalyst-supported carbon nanotube in (b) are shown in fig. 2.
Example 3
This example serves to illustrate the preparation of the supported catalyst of the present invention.
The active component and the supported catalyst were prepared as in example 1, except that: (a) the roasting temperature in the process is 1400 ℃, and the roasting time is 3 hours. To prepare the supported catalyst C.
The zirconium content of catalyst C was found to be 1.79%.
(a) The electron micrograph of the carbon nanotube after the treatment in (b) and the electron micrograph of the catalyst-supported carbon nanotube in (b) are shown in FIG. 3.
Comparative example 1
The active component and the supported catalyst were prepared as in example 1, except that: (a) the step (b) is carried out directly with the dried carbon nanotubes without baking. To prepare the supported catalyst D.
The zirconium content of catalyst D was found to be 1.76%.
(a) An electron micrograph of the carbon nanotube after the treatment in (b) and an electron micrograph of the catalyst-supported carbon nanotube in (b) are shown in fig. 4.
Example 4
This example serves to illustrate the reaction effect of the supported catalyst of the present invention.
200ml of toluene, 5.25ml of a 2.0 mol/l hexane solution of trichlorotriethylaluminum and 3.45ml of a 1.0 mol/l toluene solution of triethylaluminum were sequentially added to the reaction system under anhydrous and oxygen-free conditions, and supported catalyst A was added so that the molar ratio of Al/Zr was 27. Introducing ethylene, reacting for 1 hour under the conditions of 3.0MPa and 80 ℃, reducing the temperature of the system to 25 ℃ after the reaction is finished, discharging gas products, collecting liquid products, adding 10ml of 0.5 mol/L sodium hydroxide ethanol solution to terminate the reaction, washing with water for three times, and drying with anhydrous magnesium sulfate to obtain oligomerization products. The catalyst activity and the distribution of the oligomerization products are shown in Table 1.
Example 5
This example serves to illustrate the reaction effect of the supported catalyst of the present invention.
The ethylene oligomerization was carried out as in example 4, except that: the catalyst B prepared in example 2 was used. The catalyst activity and the distribution of the oligomerization products are shown in Table 1.
Example 6
This example serves to illustrate the reaction effect of the supported catalyst of the present invention.
The ethylene oligomerization was carried out as in example 4, except that: catalyst C prepared in example 3 was used. The catalyst activity and the distribution of the oligomerization products are shown in Table 1.
Comparative example 2
The ethylene oligomerization was carried out as in example 4, except that: the catalyst D prepared in comparative example 1 was used. The catalyst activity and the distribution of the oligomerization products are shown in Table 1.
Comparative example 3
The ethylene oligomerization was carried out as in example 4, except that: the active ingredient prepared in example 1 was used directly. The catalyst activity and the distribution of the oligomerization products are shown in Table 1.
Example 7
This example serves to illustrate the reaction effect of the supported catalyst of the present invention.
The ethylene oligomerization was carried out as in example 4, except that: the ethylene pressure was 8 MPa. The catalyst activity and the distribution of the oligomerization products are shown in Table 1.
Example 8
This example serves to illustrate the reaction effect of the supported catalyst of the present invention.
The ethylene oligomerization was carried out as in example 4, except that: the ethylene pressure was 12 MPa. The catalyst activity and the distribution of the oligomerization products are shown in Table 1.
TABLE 1
Figure BDA0001343269440000111

Claims (12)

1. A load type ethylene oligomerization catalyst is characterized in that a carrier is a carbon nano tube, and active components are selectively loaded in the carbon nano tube; wherein the active component is formed by ZrX4Is prepared by reaction with C3-C8 alkanol; the preparation method of the supported ethylene oligomerization catalyst comprises the following steps: (1) in an inert solvent, ZrX4Reacting with C3-C8 alkanol to obtain a solution; (2) fully contacting the solution prepared in the step (1) with the roasted carbon nano tube; the roasting temperature of the carbon nano tube is 1000-1400 ℃, and the roasting time is 1-10 h.
2. Catalyst according to claim 1, characterized in that in the reaction for preparing the active component, an alkanol is reacted with ZrX4The molar ratio of (a) to (b) is 3:1 to 9: 1.
3. The catalyst according to claim 1, wherein the carbon nanotubes have a tube diameter of 5nm to 30 nm.
4. The catalyst according to claim 1, wherein the carbon nanotubes have a tube diameter of 8nm to 25 nm.
5. The catalyst according to claim 1, wherein the carbon nanotubes have a tube diameter of 8nm to 15 nm.
6. The catalyst according to claim 1, wherein the Zr content is 0.5 to 20% based on the mass of the catalyst.
7. The catalyst of claim 1, wherein the carbon nanotubes are pretreated prior to calcination, the pretreatment comprising: placing the carbon nano tube in mixed acid of sulfuric acid and nitric acid, and treating for 1-10 h; the mass concentration of the sulfuric acid is greater than 95%, the mass concentration of the nitric acid is greater than 60%, and the volume ratio of the sulfuric acid to the nitric acid is 0.5: 1-5: 1.
8. The catalyst according to claim 1, wherein in the pretreatment method, the volume ratio of sulfuric acid to nitric acid is 1:1 to 4: 1.
9. The catalyst according to claim 1, wherein in the pretreatment method, the volume ratio of sulfuric acid to nitric acid is 2.5:1 to 3.5: 1.
10. A process for oligomerization of ethylene to linear alpha-olefins, characterized in that ethylene is oligomerized to linear alpha-olefins in an inert solvent in the presence of the supported catalyst of claim 1 and an aluminum alkyl co-catalyst.
11. The method according to claim 10, wherein the molar ratio of aluminum to zirconium is 1:1 to 200:1, the oligomerization temperature is 20 ℃ to 200 ℃, and the ethylene pressure is 0.1MPa to 20 MPa.
12. The process according to claim 10 or 11, wherein the ethylene pressure is from 8MPa to 20 MPa.
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