CN117399054A - Preparation method and application of olefin epoxidation catalyst - Google Patents

Preparation method and application of olefin epoxidation catalyst Download PDF

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Publication number
CN117399054A
CN117399054A CN202311380529.6A CN202311380529A CN117399054A CN 117399054 A CN117399054 A CN 117399054A CN 202311380529 A CN202311380529 A CN 202311380529A CN 117399054 A CN117399054 A CN 117399054A
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zsm
reaction
olefin
catalyst
epoxidation catalyst
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赵琳
詹红菊
张万珍
刘善培
施红
曹欣洋
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Jingchu University of Technology
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Jingchu University of Technology
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method and application of an olefin epoxidation catalyst, wherein the preparation method of the olefin epoxidation catalyst comprises the following steps: ZSM-5 and Co (Ac) were first prepared 2 ·4H 2 O is pre-reacted in ethanol, then alkaline compound is added for reaction, ethanol in the reaction liquid is removed after the reaction is finished, and the catalyst is obtained after drying treatment. The method takes ZSM-5 as a carrier, and can synthesize the catalyst CoO under the condition of no heating x ZSM-5, and CoO in the resulting catalyst x The particle size is small, the dispersibility is good, the stability is high, and a richer active site is provided for the epoxidation reaction of olefin and oxygen molecules, so that the epoxidation reaction of olefin is promotedThe catalyst has good application prospect.

Description

Preparation method and application of olefin epoxidation catalyst
Background
The invention belongs to the technical field of catalytic materials, and particularly relates to a preparation method of an olefin epoxidation catalyst and application of the olefin epoxidation catalyst in catalyzing olefin epoxidation reaction.
Background
Epoxidation of olefins plays an important role in the chemical industry, and in recent years, more and more people have studied catalytic epoxidation, but most people use H 2 O 2 The oxidation of olefins with an isooxidant is not a few reports of direct oxidation of olefins with air. In addition, noble metals are mostly selected as catalysts for the catalytic epoxidation reaction, and the noble metals are expensive, so that the production cost is increased. And the productivity is not high, the environment is easy to be polluted, the production cost is greatly increased even if the catalyst is recycled, and the method is not suitable for industrialized mass production.
Microporous zeolite is an important carrier in chemical catalytic epoxidation reaction, and the pore canal is regulated to reach the maximum optimal load rate by means of its unique spatial pore canal structure. The ZSM-5 is a molecular sieve which has a uniform structure and large specific surface area, is a novel structure zeolite molecular sieve with high silicon three-dimensional cross straight channels, belongs to an orthorhombic system, has the characteristics of oleophylic and hydrophobic properties and high hydrothermal stability, and has great advantages as a carrier of active metal. ZSM-5 has a size of 5.1X15.5 and compared with conventional microporous zeolite and MCM-41This spatial structural feature determines the catalytic performance of the support, on the other hand, the catalytic performance of the catalyst also depends on the number and type of acid sites of the catalyst.
The prior researches show that when metal Fe or other active metals are introduced into ZSM-5, the catalyst shows good catalytic performance under the synergistic effect of the active metals and ZSM-5. The prior art uses ZSM-5 as a carrier to directly load active metal cobalt and apply the active metal cobalt in photocatalysis or molecular oxygen catalysis reaction. But there are few applications of ZSM-5 as a support to support active metallic cobalt and to catalytic epoxidation of olefins.
Disclosure of Invention
In view of the above, the invention aims to construct a catalyst loaded with cobalt metal oxide particles by using a ZSM-5 molecular sieve as a carrier, and the catalyst is convenient to recycle, and the loaded cobalt metal oxide particles have small size, good dispersibility and high stability; when the obtained catalyst is used for the catalytic epoxidation reaction of olefin, the catalyst has the advantages of high reactant conversion rate and good selectivity.
The technical scheme of the invention is as follows:
a process for preparing an olefin epoxidation catalyst comprising the steps of:
s1, ZSM-5 and Co (Ac) 2 ·4H 2 O is pre-reacted in ethanol, and then an alkaline compound is added for reaction;
s2, removing ethanol in the reaction liquid obtained in the step S1, and drying to obtain an olefin epoxidation catalyst;
wherein the alkaline compound is any one or more of potassium carbonate, sodium bicarbonate, anhydrous dipotassium hydrogen phosphate, sodium silicate, ammonium carbonate, ammonium bicarbonate, aluminum hydroxide, copper hydroxide, quaternary ammonium base, silver diammine hydroxide, chalcanthitum, sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium persulfate.
In the preparation method, cobalt acetate is used as a cobalt source, alkali is added into an alcohol solution of the cobalt acetate to generate cobalt metal oxide in one step, meanwhile, the generated oxide is directly loaded on a carrier, and the size of oxide particles is limited by utilizing the space structure of a molecular sieve, so that the aggregation of the cobalt metal oxide is effectively avoided, and the generated oxide particles are smaller in size, better in dispersibility and higher in stability. In addition, the main component of the cobalt metal oxide particles of the invention is Co 3 O 4 May contain a small amount of Co 2 O 3 And/or CoO.
In the above preparation method, ZSM-5 may be subjected to an activation treatment before it is added to ethanol. The activation treatment mode is preferably as follows: and (3) roasting ZSM-5 at 500-550 ℃ for 5-10h under the air condition.
In the above preparation method, ZSM-5 and Co (Ac) 2 ·4H 2 The mass ratio of O is preferably (0.05-0.15): 1, and the conditions for the pre-reaction are preferably: reacting for 1-2h at 0-30 ℃. More preferably, the pre-reaction may be carried out under stirring and/or ultrasound conditions.
In the above preparation method, the amount of the basic compound added is preferably 20 to 80wt% based on the mass of ZSM-5.
In the above preparation method, the reaction conditions after adding the active ingredient base in step S1 are preferably: reacting for 6-24h at 0-30 ℃; more preferably, the reaction time is 12 to 24 hours.
In the preparation method, in the step S2, ethanol can be removed by adopting rotary steaming treatment, and the obtained product is heated for 12-24 hours at the temperature of 90-110 ℃ to obtain the stable dispersed olefin epoxidation catalyst.
The olefin epoxidation catalyst prepared by the method also belongs to the protection scope of the invention.
Based on the olefin epoxidation catalyst prepared by the invention, the invention further provides application of the catalyst in catalyzing olefin to undergo epoxidation reaction, and the catalyst is specifically as follows: air is used as an oxidant, and olefin is subjected to epoxidation reaction under the action of the catalyst.
In the above application, the olefin is preferably one or more of alpha-pinene, beta-pinene, styrene, cyclohexane, 1-octene, limonene and cyclooctene.
In the above applications, the temperature of the epoxidation reaction is preferably 40 to 90 ℃.
More preferably, the catalyst is used in an amount of from 0.05mol to 0.5mol of olefin per g of catalyst, and the epoxidation reaction is carried out for a period of from 4 to 10 hours.
In the above applications, small amounts of initiators, such as TBHP (t-butyl hydroperoxide), may also be added to the epoxidation system.
The beneficial effects of the invention are as follows:
the ZSM-5 used in the preparation of the olefin epoxidation catalyst is a green and environment-friendly reagent, has little environmental pollution, is an industrial product and has low price; the unique space structure of ZSM-5 avoids aggregation of active cobalt metal particles, so that the active particles can exist stably for a long time, and ZSM-5 has super-strong loading capacity, thereby improving the conditions for efficient catalytic epoxidation of the catalyst.
The invention synthesizes cobalt metal oxide (CoO) in one step by directly adding proper amount of alkali into alcohol solution of cobalt metal under normal temperature x ) Compared with high-temperature synthesis and other methods, the method not only saves energy, but also saves CoO x Is easier to prepare. The invention synthesizes CoO in one step x At the same time, coO is prevented by utilizing the micropore structure of ZSM-5 x Aggregation of particles to give CoO x The particles have smaller size and better dispersibility in the carrier, so that the active sites of the active metal are increased, and the catalytic reaction effect is further improved.
Drawings
FIG. 1 shows CoO prepared according to the present invention x XRD characterization result diagram of ZSM-5 catalyst, H-ZSM-5 is acidified ZSM-5, na-ZSM-5 is ZSM-5 after H ion in H-ZSM-5 is replaced by Na ion;
FIG. 2 shows CoO prepared according to the present invention x TEM image of ZSM-5 catalyst.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following examples. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In the following examples, unless otherwise specified, the methods are conventional; the reagents and materials described, unless otherwise specified, are commercially available.
Example 1
Co (Ac) is used in this example 2 ·4H 2 O is cobalt source, ZSM-5 is used as carrier, and CoO is prepared x -a ZSM-5 catalyst, and catalyzing the epoxidation of alpha-pinene with the catalyst obtained, the specific procedure being as follows:
(1) And placing the ZSM-5 carrier in a crucible, and placing the ZSM-5 carrier in a tubular roasting furnace for activation for 5 hours at 500 ℃ under the air condition to obtain the activated ZSM-5 carrier.
(2) 3.5g of activated ZSM-5, 1.8mmol of Co (Ac) were successively added 2 ·4H 2 Placing O and 20mL of ethanol into a flat-bottomed flask, stirring for 1h at normal temperature, and performing ultrasonic treatment for 30min; 45mmol of NaOH is added into 10mL of ethanol solution, ultrasonic treatment is carried out until the NaOH is dissolved, the obtained NaOH solution is slowly dripped into the reaction solution (10 min), stirring is continued for 12h at normal temperature, and the solution turns from gray to black brown.
(3) Performing rotary evaporation on the final reaction liquid obtained in the step (2) (ethanol solution with the temperature of 60-70 ℃ is evaporated under the pressure of 0.08 MPa) to obtain black brown solid; washing with ethanol and distilled water three times in sequence to remove excessive Ac － And other impurities, drying the obtained solid at 100deg.C for 15 hr to obtain catalyst, and recording as CoO x -ZSM-5。
(4) Weighing the Co in a three-necked flask 3 O 4 30mg of ZSM-5 catalyst and alpha-pinene 3mmol,TBHP 0.3mmol,DMF10g are stirred uniformly at normal temperature, then are put into an oil bath for reaction, and a proper amount of air is introduced through an air generator, wherein the air flow rate is 45mL/min, the reaction temperature is 85 ℃, and the reaction time is 5h.
The corresponding peaks of the reactants, the main products and the byproducts are measured by a gas chromatograph, and the selectivity and the conversion rate of the reaction are calculated. Reaction detection conditions: the reaction was monitored by GC-1300 using chlorobenzene as an internal standard. Gas chromatography conditions: the capillary column is ZKAT-5 (30 m multiplied by 0.25mm multiplied by 0.25 nm), the carrier gas is N2, and the split ratio is 50:1; the vaporization chamber temperature was 260 ℃, the initial column box temperature was 70 ℃, the programmed temperature was increased, and the detector temperature was 280 ℃.
Results CoO x The conversion rate of the-ZSM-5 catalyzed alpha-pinene reaches 97.70mol percent, and the selectivity of the epoxy product is improvedUp to 90.05%.
In addition, for the catalyst CoO prepared in this example x ZSM-5 was XRD and TEM characterized. XRD characterization results (see fig. 1) showed that: ZSM-5 supported CoO in example 1 x Loaded CoO x No effect was then exerted on the ZSM-5 crystal structure. From the TEM image (FIG. 2), it is evident that the particles with a size of 3-10nm (CoO of quantum dot size x ) It can be inferred that CoO x The crystals were uniformly distributed in ZSM-5.
Comparative example 1
In this example, coCl 2 ·6H 2 O is a cobalt source, ZSM-5 is used as a carrier to prepare a catalyst, and the catalyst is used for catalyzing the epoxidation reaction of alpha-pinene, and the specific process is as follows:
(1) And placing the ZSM-5 carrier in a crucible, and placing the ZSM-5 carrier in a tubular roasting furnace for activation for 5 hours at 500 ℃ under the air condition to obtain the activated ZSM-5 carrier.
(2) 3.5g ZSM-5, 1.8mmol CoCl were successively added 2 ·6H 2 Placing O and 20mL of ethanol into a flat-bottomed flask, stirring for 1h at normal temperature, and performing ultrasonic treatment for 30min; 45mmol of NaOH is added into 10mL of ethanol solution, ultrasonic treatment is carried out until the NaOH solution is dissolved, the NaOH solution is slowly dripped into the reaction solution (10 min), stirring is continued for 12h at normal temperature, and the solution is changed from gray to black brown.
(3) Performing rotary evaporation on the final reaction liquid obtained in the step (2) (ethanol solution with the temperature of 60-70 ℃ is evaporated under the pressure of 0.08 MPa) to obtain black brown solid; washing with ethanol and distilled water three times in sequence to remove excessive Cl － And other impurities, drying the obtained solid at 100deg.C for 15 hr, and marking the obtained catalyst as CoO x -ZSM-5-Cl。
(4) CoO was weighed in a three-necked flask x 30mg of ZSM-5-Cl catalyst, and alpha-pinene 3mmol,TBHP 0.3mmol,DMF10g are stirred uniformly at normal temperature, then are put into an oil bath for reaction, and a proper amount of air is introduced through an air generator, wherein the air flow rate is 45mL/min, the reaction temperature is 85 ℃, and the reaction time is 5h.
The conversion and selectivity were measured and calculated as in example 1, and the results showed that the catalyst obtained in this example gave a conversion of 60.21mol% of α -pinene and a selectivity of 89.23% of the epoxide product.
As can be seen from example 1 and comparative example 1, the catalytic performance of the catalyst prepared using cobalt chloride as the cobalt source is far lower than that of the catalyst prepared using cobalt acetate as the cobalt source, mainly because: in the preparation method of the invention, different cobalt sources influence CoO x Crystal formation, coO synthesized with cobalt acetate as cobalt source x The crystal particles are complete and the crystals are uniformly distributed in ZSM-5, while the chloride ions in comparative example 1 directly affect the synthesis of the crystals, thereby reducing the active sites of the catalyst and causing the undesirable catalytic effect.
Comparative example 2
In the method, ZSM-5 is directly used as a catalyst to catalyze the epoxidation reaction of alpha-pinene, and the specific process is as follows:
30mg of ZSM-5 catalyst and alpha-pinene 3mmol,TBHP 0.3mmol,DMF10g are weighed in a three-neck flask, stirred uniformly at normal temperature, then put in an oil bath for reaction, and a proper amount of air is introduced through an air generator, wherein the air flow rate is 45mL/min, the reaction temperature is 85 ℃, and the reaction time is 5 hours.
The conversion and selectivity were measured and calculated as in example 1, and the result showed that the ZSM-5 catalyzed α -pinene conversion was only 10.31mol% and the selectivity of the epoxide product reached 87.28%.
Comparative example 3
In this example, co (Ac) 2 ·4H 2 O is a cobalt source, na-X is used as a carrier to prepare a catalyst, and the catalyst is used for catalyzing the epoxidation reaction of alpha-pinene, and the specific process is as follows:
(1) The Na-X carrier is activated by the same method, namely the Na-X carrier is placed in a crucible, and is put in a tube type roasting furnace for 5 hours at 500 ℃ under the air condition, so that the activated Na-X carrier is obtained.
(2) 3.5g of Na-X, 1.8mmol of Co (Ac) were successively added 2 ·4H 2 Placing O and 20mL of ethanol into a flat-bottomed flask, stirring for 1h at normal temperature, and performing ultrasonic treatment for 30min; adding 45mmol NaOH into 10mL ethanol solution, ultrasonic treating to dissolve, slowly (10 min) dripping NaOH solution into the reaction solution, and stirring at normal temperature for 12 hrChanging from grey to black brown.
(3) Performing rotary evaporation on the final reaction liquid obtained in the step (2) (ethanol solution with the temperature of 60-70 ℃ is evaporated under the pressure of 0.08 MPa) to obtain black brown solid; washing with ethanol and distilled water three times in sequence to remove excessive Ac － And other impurities, drying the obtained solid at 100deg.C for 15 hr, and marking the obtained catalyst as CoO x -Na-X。
(4) Weighing the above CoO in a three-necked flask x 30mg of Na-X catalyst and 3mmol,TBHP 0.3mmol,DMF10g of alpha-pinene are stirred uniformly at normal temperature and then put into an oil bath for reaction, and a proper amount of air is introduced through an air generator, wherein the air flow rate is 45mL/min, the reaction temperature is 85 ℃, and the reaction time is 5h.
Conversion and selectivity were measured and calculated as in example 1, indicating CoO x The conversion rate of the Na-X catalyzed alpha-pinene reaches 85.92mol percent, and the selectivity of the epoxy product reaches 79.76 percent.
The upper and lower limits and interval values of the substances, the upper and lower limits and interval values of the process parameters can be all used for realizing the invention, and are not listed here.
In conclusion, the invention takes ZSM-5 as a carrier and synthesizes CoO in one step while loading x The method not only solves the problems of Co 3 O 4 The catalyst has the problems of large catalyst dosage and difficult recycling, and CoO is controlled by utilizing the ZSM-5 molecular sieve x Particle size and CoO avoidance x The particles are aggregated, so that the obtained olefin epoxidation catalyst has the advantages of high reactant conversion rate and good selectivity.
The foregoing description of the preferred embodiments of the present invention should not be taken as limiting the scope of the invention, and it should be noted that any modifications, equivalents, improvements and others within the spirit and principles of the present invention will become apparent to those of ordinary skill in the art.

Claims (10)

1. A process for preparing an olefin epoxidation catalyst comprising the steps of:
s1, ZSM-5 and Co (Ac) 2 ·4H 2 O is pre-reacted in ethanol, and then an alkaline compound is added for reaction;
s2, removing ethanol in the reaction liquid obtained in the step S1, and drying to obtain a catalyst;
wherein the alkaline compound is one or more of potassium carbonate, sodium bicarbonate, anhydrous dipotassium hydrogen phosphate, sodium silicate, ammonium carbonate, ammonium bicarbonate, aluminum hydroxide, copper hydroxide, quaternary ammonium base, diammine silver hydroxide, chalcanthitum, sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium persulfate.
2. The method for preparing olefin epoxidation catalyst according to claim 1, wherein the ZSM-5 is an activated ZSM-5, and the activation is performed by: and (3) roasting ZSM-5 at 500-550 ℃ for 5-10h under the air condition.
3. The method for preparing olefin epoxidation catalyst according to claim 1, wherein said ZSM-5 is mixed with Co (Ac) 2 ·4H 2 The mass ratio of O is (0.05-0.15) 1, and the pre-reaction conditions are as follows: reacting for 1-2h at 0-30 ℃.
4. The method for preparing olefin epoxidation catalyst according to claim 1, wherein the basic compound is added in an amount of 20 to 80 wt.% of ZSM-5 in step S1.
5. The method for preparing an olefin epoxidation catalyst according to claim 4, wherein the reaction conditions in step S1 are: reacting for 6-24h at 0-30 ℃.
6. The method for preparing an olefin epoxidation catalyst according to claim 1, wherein step S2 uses a spin-steaming treatment to remove ethanol, and the drying treatment is carried out at a temperature of 90-110 ℃.
7. An olefin epoxidation catalyst prepared according to any of claims 1-6.
8. Use of the olefin epoxidation catalyst according to claim 7 for catalyzing the epoxidation of an olefin, wherein air is used as the oxidant, and wherein the olefin is subjected to the epoxidation reaction under the action of the olefin epoxidation catalyst.
9. The use according to claim 8, wherein the olefins comprise α -pinene, β -pinene, styrene, cyclohexane, 1-octene, limonene and cyclooctene.
10. The use according to claim 8, wherein the temperature of the epoxidation reaction is 40-90 ℃.
CN202311380529.6A 2023-10-23 2023-10-23 Preparation method and application of olefin epoxidation catalyst Pending CN117399054A (en)

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