CN113083373A - Chromia catalyst for synthesizing 1-hexene by ethylene trimerization and preparation and application thereof - Google Patents
Chromia catalyst for synthesizing 1-hexene by ethylene trimerization and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a chromite catalyst for synthesizing 1-hexene through ethylene trimerization, and a preparation method and an application thereof, wherein raw materials for preparing the chromite catalyst comprise chromite organic acid salt, electron donor, 2, 5-dimethylpyrrole and multidentate PNP compound, and at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, chlorodiethylaluminum, dichloroethylaluminum, ethyl aluminum sesquichloride, methylaluminoxane, modified methylaluminoxane and ethylaluminoxane. The chromite catalyst provided by the invention adopts a chromite source to synthesize the chromite organic metal compound, and the generated catalyst reduces the step of reducing trivalent chromium into chromite by using alkyl aluminum, so that the active centers are all +2, the loss of the catalyst is avoided, and the excessive alkyl aluminum is avoided from reducing the selectivity of the reaction and influencing the product yield. So as to develop the 1-hexene with high activity and good selectivity and greatly reduce the running cost of the 1-hexene device.
Description
Technical Field
The invention relates to a catalyst system, in particular to a chromia catalyst for synthesizing 1-hexene by ethylene trimerization, and preparation and application thereof.
Background
1-hexene is an important comonomer of low-pressure polyethylene, polyethylene resin prepared by taking 1-hexene as a comonomer has excellent tensile strength and tear strength, the quality of the polyethylene resin can be greatly improved, and 1-hexene is mainly used as the comonomer of polyethylene in foreign countries, Europe, America and the like.
In the traditional production method, products in the ethylene non-selective oligomerization process are in Schulz-Flory distribution, the selectivity of specific components is poor, and corresponding high-purity linear alpha-olefin can be obtained only through a separation process with high energy consumption, which cannot meet the increasing demand of industry on the specific alpha-olefin. In recent years, the research on ethylene selective oligomerization technology has been greatly developed. In 2003, Phillips company realized the industrial production of 1-hexene by ethylene trimerization in Katalr.
At present, in ethylene selective oligomerization catalysts, chromium-based catalysts, titanium-based catalysts, tantalum-based catalysts and the like have good performances, wherein the Cr-based catalysts have better activity and selectivity, and are more and more concerned by researchers.
The mechanism of ethylene trimerization Cr-based catalyst was proposed by Manyie in 1977. The Manyie mechanism considers that: the chromite coordination active center collides with two molecules of ethylene to form a chromite metal five-membered ring structure which is very stable and generally cannot be decomposed. It can react with one molecule of ethylene to generate an unstable butenyl-chromite-ethyl structure, and then the metal cation undergoes self-reduction elimination reaction to release one molecule of 1-hexene, as shown in figure 1.
Briggs et al by Phillips corporation proposed another Phillips mechanism model: like the Manyie mechanism, the chromia coordination active center firstly collides with two molecules of ethylene to form a stable chromia metal five-membered ring structure, the intermediate product continuously reacts with one molecule of ethylene to form an unstable metal seven-membered ring structure, and finally the seven-membered ring generates one molecule of 1-hexene through a beta-H elimination reaction, as shown in figure 2.
Both mechanisms are believed to be that an important intermediate, "five-membered ring metal", is formed during trimerization, a divergence in the way "five-membered ring metal" reacts with the third molecule of ethylene: briggs considers that the third molecule of ethylene can be inserted into a metal five-membered ring and forms a seven-membered ring structure, and one molecule of 1-hexene is generated through a beta-H elimination reaction; and Manyie considers that ethylene attacks a five-membered ring of the metal, so that a butenyl-chromite-ethyl structure is formed, and finally, chromite is eliminated through self-reduction to generate one molecule of 1-hexene.
The ethylene trimerization reaction produces a byproduct, namely mixed decene, in addition to the main product 1-hexene. It is generally believed that: the byproduct mixed decene is generated by the reaction of 1-hexene and an intermediate product, namely a chromite metal five-membered ring. By combining the two mechanisms, the formation process of each component in the mixed decene is analyzed and found out: the Manyie mechanism fails to explain the formation of n-decene-5; the Briggs mechanism fails to explain the formation of n-decene-1, and the presence of both products suggests: the above models of mechanism all exist in the ethylene trimerization process, only in different ratios.
EP699648 reports a chromium-based catalyst consisting of a chromium salt A, an organoaluminum compound B, a pyrrole compound C and a D (IIIB) chloride or an E (VIB) chloride. The most preferred chromium salts are chromium 2-ethylhexanoate and chromium naphthenate, chromium acetylacetonate. A. B, D affect catalytic activity; c affects 1-hexene selectivity. The selectivity of 1-hexene is 80 percent, and the purity is 98-99 percent. It features that 1-hexene is used as catalyst for preparing and trimerizing ethylene, so saving the apparatus and cost for separating 1-hexene from solvent.
EP 0608447a reports a chromium-based catalyst composition as a catalyst for oligomerization and/or copolymerization of ethylene, wherein a chromium-containing compound is used as one of the components of the catalyst composition; using a pyrrole compound as the second component of the chromium-based catalyst composition; a Lewis acid and/or a metal alkyl compound is used as an activator as the third component of the catalyst composition; it is also pointed out that the catalyst system may optionally contain a halogen source as the fourth component of the catalyst composition, the halogen source may be an inorganic halide or a wide variety of organic halides, and the catalyst has high selectivity to 1-hexene but low catalytic activity.
The use of Sn (OSO2F3)2 compounds in JP 0832519 in place of the halogen source of the fourth component in EP 0608447a results in a new quaternary chromium-based catalyst composition, the activity and selectivity of which are not significantly improved.
USP 5,910,619 reports that 1,2,3,4,5, 6-hexachlorocyclohexane is used as a modifier to form a quaternary catalyst composition, and the activity of the catalyst is improved; chinese patent "a catalyst for ethylene oligomerization to prepare 1-hexene" and application thereof "(CN 1294109A) uses a novel catalytic system, and the catalytic activity is obviously improved. But still not satisfactory, further improvement of the catalyst performance is desired to improve the catalytic activity.
Therefore, it is an urgent problem to develop 1-hexene having high activity and to reduce the running cost of a 1-hexene plant.
Disclosure of Invention
The invention aims to provide a chromia catalyst for synthesizing 1-hexene by ethylene trimerization, and preparation and application thereof, so as to develop 1-hexene with high activity and greatly reduce the running cost of a 1-hexene device.
In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:
according to a first aspect of embodiments of the present invention, a chromite catalyst for synthesizing 1-hexene by ethylene trimerization is provided, wherein raw materials for preparing the chromite catalyst include a chromite organic acid salt, an electron donor, 2, 5-dimethylpyrrole and a multidentate PNP compound, and at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminoxane, modified methylaluminoxane and ethylaluminoxane;
the general formula of the multi-tooth PNP compound is
Wherein, R1, R2, R3 and R4 are respectively any one of phenyl, benzyl and naphthyl; r5 is any one of isopropyl, butyl, cyclopropyl, cyclopentyl, cyclohexyl and fluorenyl.
The electron donor is any one or a combination of two or more of 1, 4-dichlorobenzene, 1, 2-trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene and 1, 4-dichlorobenzene, and preferably tetrachloroethane, pentachloroethane and hexachloroethane.
According to a second aspect of embodiments of the present invention, there is provided a method of preparing a chromia catalyst for the trimerisation of ethylene to 1-hexene, comprising the steps of:
(1) the components are weighed for later use according to the chromia catalyst for synthesizing 1-hexene by ethylene trimerization in the claims 1-2;
(2) and (2) mixing the components weighed in the step (1) in an inert environment to prepare the chromia catalyst for synthesizing 1-hexene by ethylene trimerization.
According to a third aspect of the embodiments of the present invention, there is provided a method for preparing 1-hexene, including the method for preparing the chromia catalyst used for ethylene trimerization to synthesize 1-hexene, further including adding the chromia catalyst prepared in step (2) and used for ethylene trimerization to synthesize 1-hexene into a reaction kettle, then introducing ethylene, and obtaining the 1-hexene after the reaction is finished.
Further, the reaction temperature of the reaction kettle is 30-150 ℃, preferably 50-130 ℃, and more preferably 100-130 ℃; the reaction time of the reaction kettle is 0.1-4 hours, preferably 0.3-1 hour, and more preferably 0.5-0.7 hour.
Further, the reaction pressure of the reaction kettle is 0.5-10.0 MPa, preferably 1-10 MPa, and more preferably 2-6 MPa;
further, the reaction kettle in the step (3) is filled with an inert solvent.
Further, the inert solvent comprises any one or the combination of more than two of alkane, aromatic hydrocarbon, halogenated hydrocarbon and olefin.
Further, the inert solvent comprises any one or the combination of more than two of benzene, toluene, xylene, isopropyl benzene, n-heptane, n-hexane, methylcyclohexane, cyclohexane, 1-hexene, octene-1 and ionic liquid.
Further, the preparation method of the chromite organic acid salt comprises the following steps:
under the anhydrous and anaerobic condition, chromocene is adopted as a raw material to react with organic acid to generate chromocene of the organic acid, and the chromocene organic acid salt is prepared after cyclopentadiene is removed by heating;
or under the condition of nitrogen protection, reacting chromium diacetate with hydrochloric acid to generate chromite chloride, and carrying out double decomposition reaction on the chromite chloride, sodium hydroxide and organic acid to generate the chromite organic acid salt;
or under the protection of nitrogen, reacting solid chromium metal with hydrochloric acid with the concentration of 20% at the temperature of 50-80 ℃ to synthesize chromite, and carrying out double decomposition reaction on the chromite, sodium hydroxide and organic acid to generate the chromite organic acid salt.
The embodiment of the invention has the following advantages: the embodiment of the invention provides a chromite catalyst for synthesizing 1-hexene by ethylene trimerization and a preparation method and application thereof, wherein the chromite catalyst adopts a chromite source to synthesize a chromite organic metal compound, and the generated catalyst reduces the step of reducing trivalent chromium into chromite by alkyl aluminum, so that active centers are ensured to be in a valence of +2, and the condition that part of the + 3-valence chromium is not reduced into the + 2-valence chromium due to the insufficient addition of the alkyl aluminum or the + 3-valence chromium is reduced into 0-valence chromium metal due to the addition of excessive alkyl aluminum is avoided. When the addition of the reducing agent is insufficient, a large amount of low molecular weight polyethylene can be generated at the + 3-valent chromium active center to influence the heat exchange of the device and block pipelines, excessive aluminum alkyl is added to reduce chromium into inactive 0-valent chromium metal, so that the loss of the catalyst is caused, and meanwhile, the excessive aluminum alkyl reduces the selectivity of the reaction and influences the yield of the product. Generally, according to the ethylene purification condition used by the device, the molar ratio of the alkyl aluminum to the metal organic compound is 150-300, the molar ratio of the chromia organic metal compound can be reduced to 30-50, the use cost of the alkyl aluminum accounts for 90% of the cost of the whole catalyst, so that the cost of the catalyst using the chromia organic metal compound is one fifth of the cost of the catalyst using the chrome organic metal compound, and the running cost of the 1-hexene device can be greatly reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a Manyie mechanism model related in the background of the invention section;
FIG. 2 is a Phillips mechanism model related to the background of the invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1. Preparation of chromium (III) isooctanoate
Under the anhydrous and anaerobic condition, chromocene is adopted as a raw material to react with isooctanoic acid to generate chromocene isooctanoate, and cyclopentadiene is removed by heating for use.
2. Preparation of the catalyst
In the warp of N2To a well-replaced 100mL stirred reactor, 10mL of dehydrated toluene, vinylidene isooctanoate (0.03mmol) synthesized in step 1,2, 5-dimethylpyrrole (29 mg), triethylaluminum (10mL), 1,1,2, 2-tetrachloroethane (7 mL,0.54 mmol) were added and reacted at room temperature for 10 min.
3. Trimerization of ethylene
A500 mL autoclave was heated to vacuum for 2 hours, purged with nitrogen several times, charged with ethylene, cooled to a predetermined temperature, and charged with dehydrated cyclohexane (200mL) and the above catalyst. Carrying out oligomerization reaction at 90 ℃ and under the pressure of 5.0MPa, cooling and releasing pressure by using ice bath after reacting for 40min, and terminating the reaction by using acidified ethanol with the mass fraction of 10%; the results are shown in Table 1.
Example 2
1. Preparation of chromium (III) isooctanoate
Under the anhydrous and anaerobic condition, the chromic diacetate reacts with hydrochloric acid to generate chromic chloride, and the chromic chloride, sodium hydroxide and isooctanoic acid undergo double decomposition reaction to generate the chromic isooctanoic acid.
2. Preparation of the catalyst
In the warp of N2A well-replaced, stirred 100mL reactor was charged with dehydrated toluene (10mL), and the chromiumisooctanoate synthesized in step 1,2, 5-dimethylpyrrole (29 mg), triethylaluminum (10mL), 1,1,2,2 tetrachloroethane (0.069mmol) reacted at room temperature for 5min before use.
3. Trimerization of ethylene
A500 mL autoclave was heated to vacuum for 2 hours, purged with nitrogen several times, charged with ethylene, cooled to a predetermined temperature, and charged with dehydrated cyclohexane (200mL) and the above catalyst. Carrying out oligomerization reaction at 20 ℃ and 5.0MPa, cooling with ice bath after reacting for 20min, relieving pressure, and terminating the reaction with acidified ethanol with the mass fraction of 10%; the results are shown in Table 1.
Example 3
1. Preparation of chromium (III) isooctanoate
Under the protection of nitrogen, solid metal chromium reacts with hydrochloric acid with the concentration of 20% at the temperature of 50-80 ℃ to synthesize chromite chloride, and the chromite chloride, sodium hydroxide and isooctanoic acid undergo double decomposition reaction to generate the chromite isooctanoate.
2. Preparation of the catalyst
In the warp of N2A well-replaced, stirred 100mL reactor was charged with dehydrated toluene (10mL), chromine isooctanoate synthesized in step 1, triethylaluminum (10mL), 1,1,2,2 tetrachloroEthane (0.069mmol) was reacted at room temperature for 5 min.
3. Trimerization of ethylene
A500 mL autoclave was heated to vacuum for 2 hours, purged with nitrogen several times, charged with ethylene, cooled to a predetermined temperature, and charged with dehydrated cyclohexane (200mL) and the above catalyst. Carrying out oligomerization reaction at 20 ℃ and 5.0MPa, cooling with ice bath after reacting for 20min, relieving pressure, and terminating the reaction with acidified ethanol with the mass fraction of 10%; the results are shown in Table 1.
Example 4
1. Preparation of chromium (III) isooctanoate
Under the anhydrous and anaerobic condition, chromocene is adopted as a raw material to react with isooctanoic acid to generate chromocene isooctanoate, and the chromocene is removed by heating for use.
2. Preparation of (Diphenyl) phosphorus Nitrogen (cyclopropyl) phosphorus (Diphenyl) ligands
(1) Preparation of N, N-diisopropyldichlorophosphoramide
In the warp of N2A well-replaced 250mL stirred reactor was charged with dehydrated toluene (100mL), PCl3(21.87mL, 0.25mol), and cooled to-20 ℃. Diisopropylamine (70 mL,0.5 mol) was added slowly with stirring at room temperature, after stirring for 3 hours, the reaction was allowed to warm to room temperature and continued for 2 hours, then filtered and dried to give 38.1g (0.19mol, 74%) of product.
(2) Preparation of phenylmagnesium bromide Grignard reagent
In the warp of N2A well-replaced 250mL stirred reactor was charged with dehydrated THF (100mL), magnesium powder (9.11g, 0.375mol), cooled in an ice bath and bromobenzene (11.775 g, 0.075 mol) was slowly added dropwise. After 2 hours, the reaction was continued for 2 hours under reflux to obtain a Grignard reagent.
(3) Preparation of diphenylphosphoryl chloride
In the warp of N2A well-replaced 250mL stirred reactor was charged with dehydrated THF (100mL), cooled to 0 deg.C and N, N-diisopropylphosphoroamidite (6.64 mL, 36 mmol) was added slowly. The reaction was allowed to warm to room temperature for 12 hours. The reaction mixture was then diluted with cyclohexane and bubbled with dry H33333l gas for 1 hour, filtered and dried to give the chlorinated diphenylPhosphorus radical.
(4) Preparation of (Diphenyl) phosphorus Nitrogen (cyclopropyl) phosphorus (Diphenyl)
In the warp of N2A fully displaced stirred 100mL reactor was charged with dehydrated dichloromethane (20mL), triethylamine (3.75 mL), diphenylphosphoryl chloride (1.326 mL, 7.2 mmol), cooled to 0 deg.C and cyclopropylamine (3.6 mmol) was added slowly. After stirring for 30min, the reaction mixture was warmed to room temperature and continued for 12 hours. Filtration and drying gave the product (0.87 g, 56.6%).
3. Preparation of the catalyst
In the warp of N2A well-replaced stirred 100mL reactor was charged with dehydrated toluene (10mL), (diphenyl) phosphazene (cyclopropyl) phosphorus (diphenyl) (29 mg), triethylaluminum (10mL), chromite isooctanoate (0.03mmol), 1,1,2, 2-tetrachloroethane (7 mL,0.54 mmol), and SiO2 (0.03mmol) and reacted at room temperature for 10min before use.
4. Trimerization of ethylene
A500 mL autoclave was heated to vacuum for 2 hours, purged with nitrogen several times, charged with ethylene, cooled to a predetermined temperature, and charged with dehydrated toluene (200mL) and the above catalyst. Carrying out oligomerization reaction at 90 ℃ and under the pressure of 5.0MPa, cooling and releasing pressure by using ice bath after reacting for 40min, and terminating the reaction by using acidified ethanol with the mass fraction of 10%; the results are shown in Table 1.
Example 5
1. Preparation of chromium (III) isooctanoate
Under the anhydrous and anaerobic condition, the chromic diacetate reacts with hydrochloric acid to generate chrominum chloride, and the chrominum chloride, sodium hydroxide and isooctanoic acid undergo double decomposition reaction to generate the chrominum isooctanoate.
2. Preparation of the catalyst
In the warp of N2A well-replaced stirred 100mL reactor was charged with dehydrated toluene (10mL), chromiumisooctanoate synthesized in step 1,2, 5-dimethylpyrrole (29 mg), the (diphenyl) phosphazene (cyclopropyl) phosphorus (diphenyl) prepared in step 2 of example 4, triethylaluminum (10mL), 1,1,2,2 tetrachloroethane (0.069mmol), and reacted at room temperature for 5min before use.
3. Trimerization of ethylene
A500 mL autoclave was heated to vacuum for 2 hours, purged with nitrogen several times, charged with ethylene, cooled to a predetermined temperature, and charged with dehydrated cyclohexane (200mL) and the above catalyst. Carrying out oligomerization reaction at 20 ℃ and 5.0MPa, cooling with ice bath after reacting for 20min, relieving pressure, and terminating the reaction with acidified ethanol with the mass fraction of 10%; the results are shown in Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Catalyst activity (g oligomer/mol Cr.h) x 107 | 5.8 | 4.1 | 6.4 | 1.6 | 5.1 |
| Butene-1 selectivity (wt%) | 0.3 | 0.4 | 0.8 | 0.4 | 0.9 |
| 1-hexene selectivity (wt%) | 95.1 | 95.2 | 95.2 | 96.3 | 97.2 |
| Polymer (wt%) | 0.02 | 0.05 | 0.04 | 0.07 | 0.02 |
The design principle of the invention is as follows:
the catalysts disclosed in the patents of EP699648, EP 0608447A, CN100402152, CN112374956A and the like for the oligomerization of ethylene to 1-hexene all employ chromium sources or organic chromium metal compounds which are trivalent chromium compounds stable under an air atmosphere. According to a famous ethylene trimerization mechanism model and a research result of many years, a chromite source is innovatively adopted to synthesize a chromite organic metal compound, and the step that aluminum alkyl reduces trivalent chromium into chromite is reduced, so that metals of active centers are all in a valence of +2, and the condition that part of the +3 valence chromium is not reduced into the +2 valence chromium when the reducing agent aluminum alkyl is not added is avoided, or the +3 valence chromium is reduced into the metal chromium in a valence of 0 when the reducing agent aluminum alkyl is added in an excessive amount. When the reducing agent is not added sufficiently, a large amount of low molecular weight polyethylene can be generated at the + 3-valent chromium active center to influence the heat exchange of a device and block pipelines, the chromium is reduced to inactive 0-valent metallic chromium by adding excessive alkyl aluminum to cause the loss of a catalyst, and meanwhile, the excessive alkyl aluminum reduces the selectivity of the reaction and influences the yield of products. Generally, according to the ethylene purification condition used by the device, the molar ratio of the alkyl aluminum to the metal organic compound is 150-300, the molar ratio of the chromia organic metal compound can be reduced to 30-50, the use cost of the alkyl aluminum accounts for 90% of the cost of the whole catalyst, and the use cost of the 1-hexene device catalyst can be reduced by using the chromia organic metal compound.
Since the chromite compound is unstable and is easily oxidized into trivalent chromium under air atmosphere, the chromite salt sold in the market at present only contains chromite diacetate, because two chromium ions of the chromite diacetate are connected through triple bonds and are not easily oxidized. The invention adopts chromium diacetate or chromocene and metal chromium as raw materials to synthesize the organic acid chromium under the protection of nitrogen. Wherein, the chromocene is expensive, and more chromium valence in the step of carrying out the replacement reaction by using the metal chromium and the acid is difficult to control, so the chromocene diacetate is preferably used as the raw material.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A chromite catalyst for the trimerization of ethylene to 1-hexene, characterised in that: the raw materials for preparing the chromite catalyst comprise chromite organic acid salt, an electron donor, 2, 5-dimethylpyrrole and a multidentate PNP compound, and at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, chlorodiethylaluminum, dichloroethylaluminum, ethyl aluminum sesquichloride, methylaluminoxane, modified methylaluminoxane and ethylaluminoxane; the general formula of the multi-tooth PNP compound is
Wherein, R1, R2, R3 and R4 are respectively any one of phenyl, benzyl and naphthyl; r5 is any one of isopropyl, butyl, cyclopropyl, cyclopentyl, cyclohexyl and fluorenyl.
2. Chromia catalyst for the trimerization of ethylene to 1-hexene according to claim 1, characterized in that: the electron donor is any one or the combination of more than two of 1, 4-dichlorobenzene, 1, 2-trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene and 1, 4-dichlorobenzene.
3. A preparation method of a chromite catalyst for synthesizing 1-hexene by ethylene trimerization is characterized by comprising the following steps:
(1) the components are weighed for later use according to the chromia catalyst for synthesizing 1-hexene by ethylene trimerization in the claims 1-2;
(2) and (2) mixing the components weighed in the step (1) in an inert environment to prepare the chromia catalyst for synthesizing 1-hexene by ethylene trimerization.
4. A process for the preparation of 1-hexene comprising the preparation of the chromia catalyst for the trimerization of ethylene to 1-hexene according to claim 3, characterized in that: adding the chromite catalyst for synthesizing 1-hexene by ethylene trimerization prepared in the step (2) into a reaction kettle, introducing ethylene, and preparing the 1-hexene after the reaction is finished.
5. The method for producing 1-hexene according to claim 4, wherein: the reaction temperature of the reaction kettle is 30-150 ℃, and the reaction time of the reaction kettle is 0.1-4 h.
6. The method for producing 1-hexene according to claim 4, wherein: the reaction pressure of the reaction kettle is 0.5-10.0 Mpa.
7. The method for producing 1-hexene according to claim 4, wherein: and (4) filling an inert solvent into the reaction kettle in the step (3).
8. The method for producing 1-hexene according to claim 7, wherein: the inert solvent comprises any one or the combination of more than two of alkane, aromatic hydrocarbon, halogenated hydrocarbon and alkene.
9. The method for producing 1-hexene according to claim 7, wherein: the inert solvent comprises any one or the combination of more than two of benzene, toluene, xylene, cumene, n-heptane, n-hexane, methylcyclohexane, cyclohexane, 1-hexene, octene-1 and ionic liquid.
10. The method for producing 1-hexene as claimed in any one of claims 4 to 9, wherein the method for producing the organic acid salt of chromite comprises:
under the anhydrous and anaerobic condition, chromocene is adopted as a raw material to react with organic acid to generate chromocene of the organic acid, and the chromocene organic acid salt is prepared after cyclopentadiene is removed by heating;
or under the condition of nitrogen protection, reacting chromium diacetate with hydrochloric acid to generate chromite chloride, and carrying out double decomposition reaction on the chromite chloride, sodium hydroxide and organic acid to generate the chromite organic acid salt;
or under the protection of nitrogen, reacting solid chromium metal with hydrochloric acid with the concentration of 20% at the temperature of 50-80 ℃ to synthesize chromite, and carrying out double decomposition reaction on the chromite, sodium hydroxide and organic acid to generate the chromite organic acid salt.
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| CN115501913A (en) * | 2022-09-22 | 2022-12-23 | 中化泉州石化有限公司 | Catalyst containing rigid structure compound and application thereof in ethylene oligomerization |
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