CN115353452B - Iron benzoate complex and preparation method and application thereof - Google Patents
Iron benzoate complex and preparation method and application thereof Download PDFInfo
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- CN115353452B CN115353452B CN202211113070.9A CN202211113070A CN115353452B CN 115353452 B CN115353452 B CN 115353452B CN 202211113070 A CN202211113070 A CN 202211113070A CN 115353452 B CN115353452 B CN 115353452B
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- BUJJNPWRTNNUCG-UHFFFAOYSA-L iron(2+);dibenzoate Chemical compound [Fe+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 BUJJNPWRTNNUCG-UHFFFAOYSA-L 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000010668 complexation reaction Methods 0.000 title description 2
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 8
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 8
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 238000006384 oligomerization reaction Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000001788 irregular Effects 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000006471 dimerization reaction Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 238000005457 optimization Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- ITAUHKJMPRCVIH-UHFFFAOYSA-K iron(3+);tribenzoate Chemical compound [Fe+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 ITAUHKJMPRCVIH-UHFFFAOYSA-K 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013179 MIL-101(Fe) Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
-
- B01J35/19—
-
- B01J35/50—
-
- B01J35/612—
-
- B01J35/613—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- 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 an iron benzoate complex and a preparation method and application thereof, and the preparation method comprises the following steps: (1) Sodium benzoate and ferric chloride are taken as raw materials and are dispersed in water to obtain a dispersion system; (2) And (3) carrying out hydrothermal treatment on the dispersion system, washing by using distilled water and ethanol, and drying to obtain the iron benzoate complex, and storing in nitrogen. The iron benzoate complex provided by the invention is flower-shaped after morphology regulation, has a large specific surface area, is beneficial to contact with more reactants, and improves the catalytic performance of the complex. Meanwhile, the material has the advantages of cheap and low-toxicity raw materials and simple preparation process.
Description
Technical Field
The invention belongs to the technical field of preparation of ethylene oligomerization catalytic materials, and particularly relates to an iron benzoate complex and a preparation method and application thereof.
Background
Ethylene oligomers are widely used in the synthesis of detergents, cosmetic auxiliaries, artificial gasoline, diesel oil and additives thereof, high-molecular polymer monomers and other chemicals, and relate to various fields of human production and life, so that the global demand is huge and gradually increased year by year. With the demands of the adoption field on various properties of materials, the selectivity of the ethylene oligomerization process is more strictly required.
The core of the ethylene oligomerization process is an oligomerization catalyst which comprises a famous Ziegler-Natta catalyst, a metallocene catalyst, a late transition metal catalyst and the like, wherein the late transition metal catalyst is used as a novel oligomerization catalyst, the eighth group metals such as Ni, co, fe and the like with rich electronic structures are used as metal centers to activate continuous growth and migration-insertion reaction, and the chain growth reaction is terminated by controlling beta-H elimination reaction to form an oligomerization product, namely the ethylene oligomer.
The eighth group metal element Fe is a transition metal with the most abundant content in the earth crust, the raw material is cheap and easy to obtain, the influence on the environment is small, and more attention is paid to the application in the field of ethylene oligomerization catalysis, so that a plurality of catalysts taking Fe as a catalytic active center are researched and developed, such as ferrocene and derivative catalysts thereof applied to reactions of asymmetric catalysis, aldol condensation, normal-pressure hydrogenation of olefin, hydrogenation of aromatic ketone, silanization and the like, and the modified catalysts are applied to ethylene oligomerization; based on the space and electronic effect of an active center in a catalytic system, the activity and selectivity of the catalyst are controlled, and Fe is matched with different ligands such as olefin, conjugated diene, benzene and the like to form a novel complex catalyst; even some researchers modify the coordination polymer containing iron to make it have oligomerization catalytic ability, for example, the organic framework material MIL-101 (Fe) containing iron is used in oligomerization catalytic process after amination modification. At present, fe-containing catalysts are in the laboratory research stage, the synthesis is complex, most of ligand molecules matched with Fe are expensive, and the Fe-containing catalysts are not suitable for industrial popularization.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an iron benzoate complex, and a preparation method and application thereof, which are synthesized by a simple hydrothermal method.
The invention realizes the purpose through the following technical scheme:
the invention provides a preparation method of an iron benzoate complex, which comprises the following steps:
(1) Sodium benzoate and ferric chloride are taken as raw materials, and are dispersed in water to obtain a dispersion system;
(2) And (3) carrying out hydrothermal treatment on the dispersion system, washing by using distilled water and ethanol, and drying to obtain the iron benzoate complex, and storing in nitrogen.
As a further optimization scheme of the invention, the mass ratio of the sodium benzoate to the ferric chloride is 1.0.
As a further optimization scheme of the invention, the hydrothermal treatment is specifically 70-180 ℃ for 48h.
As a further optimization scheme of the invention, the particle morphology of the iron benzoate complex is an irregular structure under the hydrothermal condition of less than 70 ℃, and the particle morphology of the iron benzoate complex is a tetragonal structure under the hydrothermal condition of 70-90 ℃.
As a further optimization scheme of the invention, the particles of the iron benzoate complex are of a co-vertex lamellar flower-shaped structure under the hydrothermal condition of 120-180 ℃, and the particle morphology of the iron benzoate complex is of a small-size three-dimensional flower-shaped structure under the hydrothermal condition of more than 180 ℃.
The invention provides an application of the iron benzoate complex prepared by the preparation method as an oligomerization catalyst in an ethylene oligomerization process.
The invention provides an ethylene oligomerization catalysis method, which comprises the following steps:
taking the iron benzoate complex prepared by the preparation method as a catalyst under the anhydrous and oxygen-free conditions, and mixing the catalyst with auxiliary agent methylaluminoxane and a proper amount of toluene to obtain a mixture;
(II) transferring the mixture to a reaction kettle which is subjected to dehydration and deoxidation treatment, introducing ethylene into the reaction kettle at 1.0-1.5MPa, and reacting at room temperature for 1-2h to obtain an ethylene dimerization product.
As a further optimization scheme of the invention, the aluminum-iron ratio in the step (I) is in a range of 500-700.
The invention provides a method for regulating and controlling the appearance of an iron benzoate complex, which takes benzoate and iron salt as raw materials, utilizes a hydrothermal synthesis method, and controls the appearance of the iron benzoate complex synthesized by the benzoate and the iron salt by regulating the temperature of the hydrothermal synthesis.
As a further optimization scheme of the invention, under a hydrothermal condition of less than 70 ℃, the particle morphology of the iron benzoate complex is an irregular structure, under a hydrothermal condition of 70-90 ℃, the particle morphology of the iron benzoate complex is a tetragonal structure, under a hydrothermal condition of 120-180 ℃, the particle morphology of the iron benzoate complex is a co-vertex lamellar flower-like structure, and under a hydrothermal condition of more than 180 ℃, the particle morphology of the iron benzoate complex is a small-size three-dimensional flower-like structure.
The invention has the beneficial effects that:
the tetragonal ferric benzoate complex has certain ethylene oligomerization catalytic performance, has good selectivity on ethylene dimerization products, improves the specific surface area and the catalytic performance of the flower-shaped ferric benzoate complex, and has high catalytic activity. Meanwhile, the material is simple and convenient to prepare, raw materials are easy to obtain, and the material has application potential in the aspect of industrialization.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of an iron benzoate complex having a square and flower-like structure;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of iron benzoate complexes having irregular structures and small-sized flower-like structures;
FIG. 3 is an X-ray diffraction pattern (XRD) of an iron benzoate complex;
FIG. 4 is N of iron benzoate complex 2 Isothermal desorption curve (BET);
FIG. 5 is a graph of ethylene catalytic performance of iron benzoate complexes.
Detailed Description
The present application will now be described in further detail with reference to the drawings, and it should be noted that the following detailed description is given for purposes of illustration only and should not be construed as limiting the scope of the present application, as these numerous insubstantial modifications and variations can be made by those skilled in the art based on the teachings of the present application.
1. Material
The methods used in this example are conventional methods known to those skilled in the art unless otherwise specified, and the reagents and other materials used therein are commercially available products unless otherwise specified.
2. Method of producing a composite material
2.1 iron benzoate complexes
2.1.1 preparation
Sodium benzoate and ferric chloride are placed in water according to the mass ratio of 1.0 to 3.5 for dispersion, the dispersion system is added into a hydrothermal reaction kettle, and after 48 hours of hydrothermal treatment, washing is carried out for 3 to 5 times by distilled water and ethanol and full drying is carried out respectively under the conditions that the temperature is less than 70 ℃, 70-90 ℃, 120-180 ℃ and more than 180 ℃, so as to obtain the iron benzoate complex particles.
Obtaining yellow particles with a tetragonal structure under the hydrothermal condition of 70-90 ℃; obtaining yellow particles with flower-shaped structures with common vertex lamella under the hydrothermal condition of 120-180 ℃.
2.1.2 relationship of iron benzoate Complex to temperature
As shown in FIG. 1, the SEM image shows the morphology of tetragonal iron benzoate particles (70-90 ℃) and the morphology of co-vertex lamellar flower-like iron benzoate particles (120-180 ℃).
As shown in FIG. 2, the SEM images show the morphology of irregular iron benzoate particles (< 70 ℃) and small-sized three-dimensional flower-like iron benzoate particles (> 180 ℃).
Fig. 3 is an X-ray diffraction spectrum of an iron benzoate complex, and it can be found that the formed crystal form is changed at different temperatures. Under the hydrothermal condition that the temperature is not more than 70 ℃, the iron benzoate complex is in an irregular granular shape; hydrothermal reaction at 70-90 deg.c to obtain tetragonal iron benzoate complex; under the hydrothermal condition of 120-180 ℃, the iron benzoate complex is in a flower-shaped structure with a common vertex lamella. Under the hydrothermal condition that the temperature exceeds 180 ℃, the iron benzoate complex has a flower-like structure but has smaller size.
FIG. 4 is N of iron benzoate complex 2 The isothermal adsorption-desorption curve shows that the curve types of the two iron benzoate complexes belong to the II type adsorption curve, the BET specific surface area of the irregular particles is the minimum and is 5.63m 2 (iv) a BET specific surface area of 10.10m 2 Per g, the flower-like particle iron benzoate complexes all have higher BET specific surface areas, all in the range of 18 to 20m 2 Within/g.
2.2 ethylene oligomerization catalysis Property
The iron benzoate complex obtained in 2.1.1, prepared at two temperature conditions, was stored under nitrogen.
2.2.1 preparation steps
(1) When in use, the iron benzoate complex containing 5 mu mol of Fe is taken as a catalyst to be mixed with methyl aluminoxane and proper amount of toluene under the anhydrous and anaerobic conditions, and the molar ratio of aluminum to iron is 500-700;
(2) Transferring the mixture to a reaction kettle which is subjected to dehydration and deoxidation treatment, introducing ethylene under the pressure of 1.0-1.5MPa, and reacting at room temperature for 1-2h to obtain an ethylene oligomerization catalytic product.
2.2.2 Performance testing
And (3) sampling two ethylene oligomerization catalysis products after the 2.2.1 reaction and analyzing by a gas chromatograph. As shown in fig. 5, which is a graph of ethylene catalytic performance of iron benzoate complex, the selectivity of four catalysts to ethylene dimerization product (C4) exceeds 90%, and flower-like particles have higher oligomerization activity.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (5)
1. A preparation method of an iron benzoate complex is characterized by comprising the following steps:
(1) Sodium benzoate and ferric chloride are used as raw materials and are dispersed in water to obtain a dispersion system, wherein the mass ratio of the sodium benzoate to the ferric chloride is 1.0: 3.5;
(2) Carrying out hydrothermal treatment on the dispersion system, washing the dispersion system by distilled water and ethanol, and drying to obtain an iron benzoate complex, and storing the iron benzoate complex in nitrogen;
wherein the hydrothermal treatment is carried out for 48h at 70-90 ℃ or 120-180 ℃;
under the hydrothermal condition of 70-90 ℃, the particles of the iron benzoate complex are in a tetragonal structure; under the hydrothermal condition of 120-180 ℃, the particles of the iron benzoate complex are in a common vertex lamellar flower-like structure.
2. The use of the iron benzoate complex prepared by the preparation method of claim 1 as an oligomerization catalyst in an ethylene oligomerization process.
3. The ethylene oligomerization catalysis method is characterized by comprising the following steps:
taking the iron benzoate complex prepared by the preparation method of claim 1 as a catalyst under the anhydrous and oxygen-free conditions, and mixing the catalyst with methyl aluminoxane serving as an auxiliary agent and a proper amount of toluene to obtain a mixture;
(II) transferring the mixture to a reaction kettle which is subjected to dehydration and deoxidation treatment, introducing ethylene of 1.0-1.5MPa, and reacting at room temperature for 1-2h to obtain an ethylene dimerization product.
4. The catalytic process according to claim 3, wherein the molar ratio of aluminum to iron in step (I) is in the range of 500 to 700.
5. A method for regulating and controlling the appearance of an iron benzoate complex is characterized in that sodium benzoate and ferric chloride are used as raw materials, wherein the mass ratio of the sodium benzoate to the ferric chloride is 1.0: 3.5; by utilizing a hydrothermal synthesis method and adjusting the temperature of hydrothermal synthesis, the morphology of the iron benzoate complex synthesized by the hydrothermal synthesis method and the iron benzoate complex is controlled, and the method specifically comprises the following steps: the particle morphology of the iron benzoate complex is an irregular structure under the hydrothermal condition of less than 70 ℃, the particle morphology of the iron benzoate complex is a tetragonal structure under the hydrothermal condition of 70-90 ℃, the particle morphology of the iron benzoate complex is a co-vertex lamellar flower-shaped structure under the hydrothermal condition of 120-180 ℃, and the particle morphology of the iron benzoate complex is a small-size three-dimensional flower-shaped structure under the hydrothermal condition of more than 180 ℃.
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| CN202211113070.9A CN115353452B (en) | 2022-09-14 | 2022-09-14 | Iron benzoate complex and preparation method and application thereof |
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| CN202211113070.9A CN115353452B (en) | 2022-09-14 | 2022-09-14 | Iron benzoate complex and preparation method and application thereof |
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| CN115353452A CN115353452A (en) | 2022-11-18 |
| CN115353452B true CN115353452B (en) | 2023-03-31 |
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