CN108393094A - A kind of bimetallic catalyst and its application in selectivity of styrene oxidation - Google Patents
A kind of bimetallic catalyst and its application in selectivity of styrene oxidation Download PDFInfo
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- CN108393094A CN108393094A CN201710069524.XA CN201710069524A CN108393094A CN 108393094 A CN108393094 A CN 108393094A CN 201710069524 A CN201710069524 A CN 201710069524A CN 108393094 A CN108393094 A CN 108393094A
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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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
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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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- 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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
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- 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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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The present invention relates to a kind of bimetallic catalysts, are aoxidized for selectivity of styrene.It is prepared by the following method:Alkali metal salt and vanadic salts are dissolved in deionized water, silica supports are then added and are impregnated, stand 8~for 24 hours after, then be dried, roast to get.It when being aoxidized applied to selectivity of styrene, using oxygen or air as oxidant, is passed through in reaction system by way of bubbling, under the action of bimetallic catalyst, styrene carries out catalytic oxidation with dissolved oxygen.This method catalyst preparation is simple, cheap and easy to get, when being applied to selectivity of styrene oxidation, oxidant is oxygen, safety and environmental protection, styrene conversion per pass height, the high selectivity of product benzaldehyde and Styryl oxide is not required to use solvent, the solvent-free separation puzzlement brought.
Description
Technical field
The present invention relates to a kind of bimetallic catalysts, belong to selective oxidation of olefins technical field.
Background technology
Benzaldehyde and Styryl oxide can be made in catalytic oxidation of phenylethene.Benzaldehyde is commonly called as almond oil, be it is colourless or
Yellowish transparency liquid has amygdalate smell, fragrance is used as in food, cosmetics, medicine and soap, benzaldehyde is work
The most important aromatic aldehyde of industry, it is widely used, mainly for the production of cinnamic acid, lauryl aldehyde and light green etc. and benzyl alcohol, aniline,
Benzophenone and the most basic raw material of insecticide are the most basic raw material of the certain medical products of synthesis, plastic additive, and synthesis
A kind of important intermediate of essence and flavoring agent.Styryl oxide can be used as the diluent of epoxy resin, UV- absorbents, fumet,
Be organic synthesis, pharmacy, perfume industry important intermediate, such as the bata-phenethyl alcohol that Styryl oxide Hydrogenation obtains is rose
The main component of oil, caryophyllus oil, neroli oil, and it is widely used in synthetic food, tobacco, soap and cosmetic essence.
CN102580772 discloses a kind of spherical shape V-MCM-48 catalyst, and the catalyst is used to select oxygen with hydrogen peroxide
Change styrene, obtain high styrene conversion rate and selectivity of product, by adjusting the pH of reaction solution, changes reaction product benzene
The yield of formaldehyde and Styryl oxide ratio.But the adjustment of solution ph can be brought the problem of water-oil separating in the technique, and the party
Method uses hydrogen peroxide for oxidant, and there are certain security risks.
CN101531576 discloses a kind of method preparing benzaldehyde by catalytic oxidation of phenylethene, is reaction with styrene
Object, the nanowires of gold using diameter less than or equal to 5nm is catalyst, under toluene solvant existence condition, in atmospheric oxygen atmosphere
20~48h are reacted in 80~100 DEG C, cools down, detached up to benzaldehyde after reaction.The catalyst is existed using nanocatalyst
It can meet difficulty when industry amplification, and use toluene solvant, solvent needs to recycle.
CN101885672 discloses a kind of method of preparing benzaldehyde through catalytic oxidation of styrene, with iron platinum (FePt) nanometer
Line is catalyst with one kind in toluene, dioxane, dimethylformamide, dimethyl sulfoxide (DMSO), acetonitrile or chloroform for solvent,
In oxygen atmosphere, under normal pressure, 3~32h is reacted in 50~90 DEG C, after reaction cooling, isolated benzaldehyde.
CN102757406 discloses a kind of method that epoxidation of styrene prepares Styryl oxide.This method is in titanium silicon point
Son sieve is in the presence of resin compounded modified catalyst, and using ketone as solvent, styrene carries out epoxidation reaction with hydrogen peroxide and generates ring
Oxygen vinylbenzene.It needs to use expensive Titanium Sieve Molecular Sieve in this method, and oxidant is the not high hydrogen peroxide of safety.
CN101972665 discloses a kind of epoxidation of styrene catalyst, using the mesopore molecular sieve of amino functional
SBA-15 ionic adsorptions Co2+It is prepared.Styrene, catalysts and solvents are added in stirred tank, oxygen or sky are then passed to
Gas is stirring and is being reacted under reaction temperature, then by filtering, isolating solid catalyst, liquid isolates ring by rectifying
Oxygen vinylbenzene, solvent and other byproducts.In the patent catalyst prepare it is relatively complicated, and it is follow-up involve catalyst with
The solid-liquor separation of reaction system, system processing step increase.
CN103788023 discloses a kind of new method of styrene oxidation Styryl oxide, with H2O2For oxygen source, application
Reaction-controlled phase transfer catalysis system, with toluene, tributyl phosphate, acetonitrile, dichloroethanes, ethyl acetate it is one such or two
Kind mixing is used as solvent, using ethylenediamine tetra-acetic acid (EDTA) as auxiliary agent and stabilizer.It is needed in this method actual mechanical process
Detection and the separation control for increasing EDTA, difficulty is brought to system operatio.
In the above method, mostly uses solvent and participate in reaction, difficulty is brought to the post-processing of reaction system, some oxidations
Agent additionally uses peroxide, inadequate safety and environmental protection.
Invention content
The purpose of the present invention is deficiency in the prior art, a kind of bimetallic catalyst is provided and is used for selectivity of styrene oxygen
Change, the catalyst preparation is simple, at low cost, and when being applied to selectivity of styrene oxidation, system need not use solvent, by-product
It is low, the high selectivity of Styryl oxide and benzaldehyde.
During catalytic oxidation of phenylethene prepares benzaldehyde and Styryl oxide, it will generally use metal oxide and urge
Agent, application of the metal oxide catalyst all the time in industrial catalyst is relatively broad, because its for catalysis oxidation also
Original reaction has high activity, selectivity and stability, and relative low price.And composite oxides often due to substance not
Same, the difference of ratio, carrying method not equal conditions influence, and the performance of obtained catalyst is also different.
Technical solution
A kind of bimetallic catalyst, is prepared by the following method:Alkali metal salt and vanadic salts are dissolved in deionized water,
Then silica supports are added to be impregnated, stand 8~for 24 hours after, then be dried, roast to get bimetallic catalyst;
In the bimetallic catalyst, the mass content of alkali metal is 0.1~30%;The mass content of vanadium be 0.1~
30%;Any one of the alkali metal in Li, Na, K, Rb or Cs.
Further, in the bimetallic catalyst, the mass content of alkali metal is 1~10%;The mass content of vanadium be 1~
10%.
Further, any one of the vanadic salts in ammonium metavanadate, halogenation vanadium or vanadic sulfate.
Further, the silica supports are any one in SBA-15, MCM-41 or MCM-48 mesopore molecular sieve
Kind.
Further, drying temperature is 45~90 DEG C.
Further, the calcination temperature is 400~600 DEG C, and roasting time is 8~12h.
Further, the alkali metal salt is replaced with alkali salt.Alkaline-earth metal is any one in Mg, Ca, Sr, Ba
Kind.
Application process of the above-mentioned bimetallic catalyst in selectivity of styrene oxidation:By bimetallic catalyst and styrene
Be added in reactor, be passed through oxidant and heat up reacted to get;The reaction temperature is 30~100 DEG C, the reaction time
For 2~10h, the mass ratio of the bimetallic catalyst and styrene is 0.001~0.1:1;The oxidant is air or oxygen
Gas.
In the above method, the mass ratio of the bimetallic catalyst and styrene is 0.003~0.01:1.
Advantageous effect:Compared with prior art, the present invention haing the following advantages:Catalyst preparation is simple, cheap and easy to get, answers
When being aoxidized for selectivity of styrene, system need not use solvent, product separation and post-processing simple;By-product is low, epoxy
The high selectivity of vinylbenzene and benzaldehyde;Use oxidant for oxygen, safety and environmental protection.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below, it should be noted however that the protection of the present invention
Range is not limited to these specific embodiments, but is determined by claims.
Embodiment 1
Lithium chloride 0.12g, ammonium metavanadate 0.05g are weighed, is dissolved in 2g deionized waters, is dipped into after dissolving completely
On 0.2g SBA-15 silica supports, after standing 12h, it is dried in vacuo at 50 DEG C, then by the catalyst after drying 500
8h is roasted at DEG C, obtains bimetallic catalyst.
Application of the bimetallic catalyst in selectivity of styrene oxidation:It is bis- that 0.05g is added into 100ml three-necked flasks
Metallic catalyst, 15g styrene are inserted with thermometer and bubble oxygen pipe and water cooling condenser pipe in flask.It is good stirring
Under the conditions of, it is passed through the oxygen of 100ml/min, system temperature is risen to 70 DEG C, isothermal reaction 5h.After reaction, by reactant
System carries out gas-chromatography qualitative and quantitative analysis.It is 63.1% to obtain styrene conversion rate, and benzaldehyde is selectively 69.9%, epoxy
Vinylbenzene is selectively 22.5%.
Embodiment 2
Potassium chloride 0.04g, ammonium metavanadate 0.05g are weighed, is dissolved in 2g deionized waters, is dipped into after dissolving completely
On 0.2g MCM-41 silica supports, after standing 12h, it is dried in vacuo at 50 DEG C, then by the catalyst after drying 500
8h is roasted at DEG C, obtains bimetallic catalyst.
Application of the bimetallic catalyst in selectivity of styrene oxidation:It is bis- that 0.05g is added into 100ml three-necked flasks
Metallic catalyst, 15g styrene are inserted with thermometer and bubble oxygen pipe and water cooling condenser pipe in flask.It is good stirring
Under the conditions of, it is passed through the oxygen of 100ml/min, system temperature is risen to 70 DEG C, isothermal reaction 5h.After reaction, by reactant
System carries out gas-chromatography qualitative and quantitative analysis.It is 56.2% to obtain styrene conversion rate, and benzaldehyde is selectively 68.0%, epoxy
Vinylbenzene is selectively 21.1%.
Embodiment 3
Cesium chloride 0.03g, ammonium metavanadate 0.05g are weighed, is dissolved in 2g deionized waters, is dipped into after dissolving completely
On 0.2g SBA-15 silica supports, after standing 12h, it is dried in vacuo at 50 DEG C, then by the catalyst after drying 500
8h is roasted at DEG C, obtains bimetallic catalyst.
Application of the bimetallic catalyst in selectivity of styrene oxidation:It is bis- that 0.05g is added into 100ml three-necked flasks
Metallic catalyst, 15g styrene are inserted with thermometer and bubble oxygen pipe and water cooling condenser pipe in flask.It is good stirring
Under the conditions of, it is passed through the oxygen of 100ml/min, system temperature is risen to 70 DEG C, isothermal reaction 5h.After reaction, by reactant
System carries out gas-chromatography qualitative and quantitative analysis.It is 23.1% to obtain styrene conversion rate, and benzaldehyde is selectively 86.4%, epoxy
Vinylbenzene is selectively 7.9%.
Embodiment 4
Magnesium nitrate 0.2g is weighed, is dissolved in 2g deionized waters, 0.2g MCM-48 titanium dioxides are dipped into after dissolving completely
On silicon carrier, after standing 12h, it is dried in vacuo at 50 DEG C, then the catalyst after drying is roasted into 8h at 500 DEG C, obtains list
Metallic catalyst;Vanadic sulfate 0.07g is weighed again, is dissolved in 2g deionized waters, is dipped into monometallic urging after dissolving completely
It in agent, after standing 12h, is dried in vacuo at 50 DEG C, then the catalyst after drying is roasted into 8h at 500 DEG C, obtains double gold
Metal catalyst.
Application of the bimetallic catalyst in selectivity of styrene oxidation:It is bis- that 0.05g is added into 100ml three-necked flasks
Metallic catalyst, 15g styrene are inserted with thermometer and bubble oxygen pipe and water cooling condenser pipe in flask.It is good stirring
Under the conditions of, it is passed through the oxygen of 100ml/min, system temperature is risen to 70 DEG C, isothermal reaction 5h.After reaction, by reactant
System carries out gas-chromatography qualitative and quantitative analysis.It is 10.4% to obtain styrene conversion rate, and benzaldehyde is selectively 100%.
Claims (9)
1. a kind of bimetallic catalyst, which is characterized in that it is prepared by the following method:Alkali metal salt and vanadic salts are dissolved in
In ionized waters, silica supports are then added and are impregnated, stand 8~for 24 hours after, then be dried, roast to get bimetallic
Catalyst;
In the bimetallic catalyst, the mass content of alkali metal is 0.1~30%;The mass content of vanadium is 0.1~30%;Institute
State any one of alkali metal in Li, Na, K, Rb or Cs.
2. bimetallic catalyst as described in claim 1, which is characterized in that in the bimetallic catalyst, the matter of alkali metal
It is 1~10% to measure content;The mass content of vanadium is 1~10%.
3. bimetallic catalyst as described in claim 1, which is characterized in that the vanadic salts be selected from ammonium metavanadate, halogenation vanadium or
Any one in vanadic sulfate.
4. bimetallic catalyst as described in claim 1, which is characterized in that the silica supports be selected from SBA-15,
Any one in MCM-41 or MCM-48 mesopore molecular sieves.
5. bimetallic catalyst as described in claim 1, which is characterized in that drying temperature is 45~90 DEG C.
6. bimetallic catalyst as described in claim 1, which is characterized in that the calcination temperature is 400~600 DEG C, roasting
Time is 8~12h.
7. such as claim 1 to 6 any one of them bimetallic catalyst, which is characterized in that alkali metal salt alkaline earth gold
Belong to salt to replace.
8. application process of any one of claim 1 to 7 bimetallic catalyst in selectivity of styrene oxidation, feature
Be, bimetallic catalyst and styrene be added in reactor, be passed through oxidant and heat up reacted to get;It is described
Reaction temperature is 30~100 DEG C, and the reaction time is 2~10h, and the mass ratio of the bimetallic catalyst and styrene is 0.001
~0.1:1;The oxidant is air or oxygen.
9. method as claimed in claim 8, which is characterized in that the mass ratio of the bimetallic catalyst and styrene is
0.003~0.01:1.
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CN109364932A (en) * | 2018-11-16 | 2019-02-22 | 宁夏宝丰能源集团股份有限公司 | A kind of bimetallic catalyst, preparation method and applications |
Citations (1)
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CN1800132A (en) * | 2005-01-05 | 2006-07-12 | 湖南大学 | Arene olefin catalytic oxidation for preparing aromatic aldehyde |
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CN1800132A (en) * | 2005-01-05 | 2006-07-12 | 湖南大学 | Arene olefin catalytic oxidation for preparing aromatic aldehyde |
Cited By (2)
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CN109364932A (en) * | 2018-11-16 | 2019-02-22 | 宁夏宝丰能源集团股份有限公司 | A kind of bimetallic catalyst, preparation method and applications |
CN109364932B (en) * | 2018-11-16 | 2021-09-03 | 宁夏宝丰能源集团股份有限公司 | Bimetallic catalyst, preparation method and application thereof |
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