CN108610250A - The method that anthracene oxidizing process prepares anthraquinone - Google Patents
The method that anthracene oxidizing process prepares anthraquinone Download PDFInfo
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- CN108610250A CN108610250A CN201810444253.6A CN201810444253A CN108610250A CN 108610250 A CN108610250 A CN 108610250A CN 201810444253 A CN201810444253 A CN 201810444253A CN 108610250 A CN108610250 A CN 108610250A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/04—Preparation of quinones by oxidation giving rise to quinoid structures of unsubstituted ring carbon atoms in six-membered aromatic rings
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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Abstract
The invention discloses the methods that anthracene oxidizing process prepares anthraquinone, wherein catalyst formulation：With γ Al2O3For carrier, Fe, Zr oxide are active component, and Fe γ Al are prepared using equi-volume impregnating2O3、Zr‑γ‑Al2O3Single supported catalyst and Fe Zr/ γ Al2O3Double supported catalysts.Product is analyzed using Ultra Performance Liquid Chromatography instrument, catalytic performance of the analysis of catalyst in the reaction of anthracene oxidative synthesis anthraquinone characterizes catalyst using means such as XRD.The present invention attempt exploitation solid-phase catalyst, under the conditions of normal pressure, low temperature (70 DEG C) realize anthracene catalysis oxidation prepare anthraquinone, have low energy consumption, at low cost, the advantages such as environmental-friendly.
Description
Technical field
The invention belongs to the methods that chemical technology field more particularly to anthracene oxidizing process prepare anthraquinone.
Background technology
Anthraquinone (C14H8O2) it is a kind of important fine chemicals and chemical intermediate.It is generally employed to produce Anthraquinones dye
The industrial circles such as material and high-strength hydrogen peroxide and enhancing brown paper production process, or even it is widely used in the doctors such as medicine, pesticide
Pharmaceutical field.Wherein, anthraquinone is the parent material of major class dyestuff and pigment, is occupied in synthetic dyestuffs field very importantly
Position.With fine industry diversification and go from strength to strength, demand of the anthraquinone product at home on international market shows always
Steady increased trend.In view of the huge potential market demand of anthraquinone, Optimal improvements anthraquinone process production line reduces its production
Cost improves the yield of anthraquinone to promoting the development of entire catalysis industry to have great importance, for synthesis anthraquinone catalyst
Develop dawn of taking.
It is broadly divided into according to production method anthraquinone and with TBHP, H using Phthalic Anhydride as the synthesis of representative2O2、O2Deng for oxidation
The two major classes such as the oxidation of agent is anthraquinone.Wherein the production capacity of Phthalic Anhydride synthesis anthraquinone is better than the production capacity for aoxidizing anthraquinone, but synthesizes anthraquinone
In contain micro inorganic salts, influence the purity of downstream product, and the three wastes cause environment certain injury.Oxidizing process prepares anthracene
The production technology of quinone is used widely in industrial more developed country, and the production method environmental pollution is low, entire production technology
Benefit better than the Process of synthesis anthraquinone, be more suitable for the high-grade dyestuff of production.And in recent years, coal tar processing industry in China's was sent out
Exhibition is rapid, and the rough machined industrial output of tar has reached ten thousand t/a more than 2000, and anthracene raw material supply amount is significantly promoted, especially coal
The developing direction of the chain for constantly extending its industry of tar production enterprise, production oxidation anthraquinone is determined, and has built up more sets
Technique processing unit (plant), the technique productions method green non-pollution, the occupation rate of market for aoxidizing anthraquinone keep steady ascendant trend.
One, Phthalic Anhydride synthesizes anthraquinone
1, using Lewis acid and liquid phase Bronsted acid as catalyst
The use of the Lewis acid and liquid phase Bronsted acid of higher cost is catalyst, with traditional in past ten years
Friedel-Crafts acylation reactions (Phthalic Anhydride) synthesize anthraquinone, are industrially widely used.Lewis acid and liquid phase
Bronsted acid is that the corrosivity of catalyst pollutes the environment, and production technology is more complex, and development green catalysis technology is very big
The research for strengthening Friedel-Crafts acylation reactions ensure that economic cost feasibility.Also, it helps developing newly
Green catalyst is for aromatic compounds or the Friedel-Crafts acylation reactions of aromatic compound.
Mohammad etc. report a kind of synthesis of layer aluminium silicate inorganic polymer (also referred to as contain Bronsted and
The geo-polymer in lewis acidity site) novel solid acid catalyst, the model liquid phase F-C for substituted benzene is acylated anti-
It answers, synthesis, which is realized, after catalyst passes through handles the reactions such as dealuminzation and desiliconization, enhances acidity and porosity, improves catalysis effect
Rate, geo-polymer have huge potentiality and cost-effectiveness, can hold repeatedly regeneration and reuse and not react significantly
Property loss, be readily synthesized with the heterogeneous solid catalyst of environment-friendly type be applied to fine chemistry.
2, using zeolite molecular sieve as catalyst
Claire etc. is exchanged from original H zeolites (BEA, MFI) by cation or dipping technique, is prepared for different structure
The acid catalyst of Ni, Ag and Fe loaded zeolite, catalyst activity are attributed to the density and accessibility of Bronsted acidity substance,
Key effect activated reactant has been played in the field.Original ZSM-5 zeolite is proposed to be that most possible catalyst is used for
The substance of FriedeleCrafts acylations is carried out, has highest intrinsic activity (TOF) close to 0.09h1.It replaces passing with zeolite
Friedel-Crafts acid catalysts (the BF of system3, AlCl3) technique is made more to clean, corrosivity smaller is more economical.
Wang etc. is studied synthesizing anthraquinone as catalyst using the zeolite molecular sieve of zeolite molecular sieve and modification, is studied
The result shows that carrying out benzene and phthalic anhydride friedel-crafts reaction using gas-solid heterogeneous catalytic reaction, the suitably modified zeolite molecular sieve of selection is urged
Agent, under optimum conditions of operation phthalic anhydride conversion ratio reach 59.1%, anthraquinone selectivity is up to 94.3%.
Two, oxidizing process synthesizes anthraquinone
1, anthraquinone is prepared by oxidant of TBHP
Tertbutanol peroxide (TBHP) has a very wide range of applications in organic synthesis, since the synthetic method of TBHP is more
Sample, yield are higher, become a kind of effective and cheap oxidant for preparing anthraquinone, but prepare anthracene carrying out Oxidation Anthracene using TBHP
During quinone, needs to select suitable catalyst, reaction is made to reach peak efficiency.
Kholdeeva etc. has evaluated Fe- and Cr- funds in anthracene and tertbutanol peroxide (TBHP) in liquid phase oxidation reaction
Belong to the catalytic performance of organic backbone (MOF) MIL-100 and MIL-101, wherein obtain Cr-MIL-101, Cr-MIL-100>Fe-
MIL-100>The stability of tetra- kinds of catalysis of Fe-MIL-101 reduces successively.Cr-MOFs and Fe-MIL- is used in the oxidation reaction of anthracene
101 be catalyst, and chlorobenzene is solvent at 100 DEG C, and after 1.5h, the selectivity of 9,10- anthraquinones (AQ) is in 92-100%, anthracene conversion
Rate reaches 100%.Especially in the conversion ratio of anthracene, anthraquinone selectivity and TOF aspects show excellent Cr-MIL-101 catalyst
Catalytic performance.Will not occur the leaching of active metal under optimum reaction condition, and MOF can be recycled for multiple times without
Catalytic performance can be reduced.
Ivanchikova etc. proposes a kind of method preparing anthraquinone using TBHP as oxidant, using Cr-MIL-
101 or Cr-MIL-100 is catalyst, selects optimum reaction condition：100 DEG C of reaction temperature adopts chlorobenzene and makees solvent, reaction time
4h, reaction result is ideal, and the conversion ratio of anthracene, the selectivity of anthraquinone and anthraquinone yield are 99% or more.
Selvaraj etc. describes a kind of CrSBA-15 mesopore molecular sieves and prepares anthraquinone as catalyst Oxidation Anthracene, and selection is most
Good reaction condition is：Reaction temperature is 77 DEG C, the molar ratio of TBHP and anthracene is 4:1, the mass ratio of anthracene and catalyst is 1:1, molten
Agent is benzene, and the conversion ratio of reaction time 20h, anthracene reach 90,6%, and the selectivity of anthraquinone is 100%.The catalyst has regular
Mesoporous, larger aperture 13nm, pore volume 91.11cm3/ g and specific surface area 973m2/ g shows smooth " rope " shape
State.Such catalyst has huge application potential in chemical field.
Bordoloi etc. proposes a kind of mesoporous silicate catalyst of phosphorus molybdenum vanadium heteropolyacid load, is oxidation with TBHP
Agent, at low temperature realize anthracene to anthraquinone liquid-phase conversion.Optimum reaction condition：Reaction temperature is 80 DEG C, solvent is benzene, n
(TBHP):N (anthracene)=5:1, n (anthracene):N (catalyst)=430:1, the conversion ratio of reaction time 12h, anthracene reach 60%, anthracene
The selectivity of quinone is 100%, which can realize oxidation of the anthracene to anthraquinone at low temperature, and catalyst amount is less,
It is a kind of catalyst for being applied to anthraquinone and preparing with higher economic value.
2, with H2O2Anthraquinone is prepared for oxidant
With the development of the industries such as anthraquinone, caprolactam, propylene oxide, hydrogen peroxide is by as a kind of common Industrial Green
Oxidant especially has very important status in the preparation of anthraquinone and production technology, currently, many chemical plant both at home and abroad
It is preferred that hydrogen peroxide prepares anthraquinone as Green Oxidant, since hydrogen peroxide is easily prepared, yield is higher, therefore is made using hydrogen peroxide
Anthraquinone is prepared for oxidant, also at a kind of method preparing anthraquinone of current major chemical field favor.But with industry
On demand to anthraquinone constantly increase, select suitable catalyst promoted hydrogen peroxide as oxidant prepare the efficiency of anthraquinone at
One of current anthraquinone preparation field research hotspot.
Sorokin etc. develops a kind of FePcS/H for anthracene oxidation2O2New and effective catalyst system and catalyzing, be based on multi-chlorophenol
Oxidative degradation direction, have checked the MeCN/H in four sulfonephthalein cyanines (FePcS) of iron2The benzene carried out in O mixtures is to iron or manganese
Complex anthracene oxidation prepares anthraquinone, uses cheap and " green " oxidant H2O2, catalyst concn is the concentration of 10% reactant,
PH value is 5 or so.Catalyst activity is relatively stablized, and anthraquinone yield is considerable.
Wang etc. describe it is a kind of by anthracene be oxidized to anthraquinone effective ways use three normal-butyl bromination of bromination ferric trichloride
Iron (NBPBFTC) is catalyst, H2O2As oxidant, solvent is acetonitrile, under the premise of aoxidizing 50mg anthracenes, by optimum response item
Part is determined as 50 DEG C, 45min, NBPBFTC (100mg) and H2O2(1mL).With this condition, anthraquinone yield is 99.5%.
NBPBFTC at least may be reused 2-3 times, and catalytic activity is maintained at fluctuation in a considerable range.
Jiang Xiaoping etc. synthesizes H3PW12O40、H7[P2Mo17VO62]、H8[P2Mo16V2O62]、H9[H2Mo15V3O62]、H8
[P2Mo14V4O62H2] five kinds of Dowson types heteropolyacid catalysts are catalyzed H2O2Oxidation Anthracene prepares anthraquinone.Pass through experiment, as a result table
It is bright, 5 kinds of catalyst H8[P2Mo14V4O62H2] catalytic activity highest, control anthracene and H2O2Solution proportion be 1:11, reaction temperature
70 DEG C of degree, anthraquinone yield reaches 93.2%.Intermediate waste liquid of the Dowson types heteropolyacid catalyst as a variety of Chemical Manufactures, can be with
It gathers materials on the spot development technology route, also, so preparing anthraquinone with this oxidizing process has higher economic benefit.
The discoveries such as Samanta use TBHP or H2O2Make metal silicate of the oxidant based on Fe/V/Ti and obtains product yield
It is low, in zeolite or SiO2It mixes a large amount of metals in skeleton to be difficult, the faintly acid of zeolitic frameworks makes in anthracene oxidation reaction
The selectivity of required product is low.If Fe/V/Ti base catalyst is supported on neutral carrier such as carbon or associated materials, can solve
The certainly problem such as FeVO4And g-C3N4FeVO of the nanocomposite in load 30%4Catalyst uses H2O2For oxidant oxygen
Change in anthracene reaction and shows better activity.Samanta etc. describes three kinds of semiconductor alloy vanadate FeVO4, BiVO4With
LaVO4Catalyst, liquid phase oxidation anthracene prepare anthraquinone, these catalyst can be recycled by Magnetic Isolation, research shows that FeVO4
Highest activity is shown in metal vanadate.Negligible loss activity is important for sustainable heterogeneous catalysis
, the catalytic process of exploitation has the potentiality of the various industrial important fine chemicals of sustainable synthesis.
Development trend in recent years, using H2O2It is that a kind of industry that important anthracene oxidation prepares anthraquinone is raw as oxidant
Production approach.Under the action of catalyst, for the yield of anthraquinone up to 90% or more, selectable range of catalysts is wide, efficiency activity visitor
It sees.It is a kind of selection with higher economic benefit using Dowson type heteropolyacid catalysts from the point of view of anthraquinone yield, leads to
It can also often combine with other chemical process, catalysis oxidation preparation is carried out using Dowson type heteropoly acid waste liquids.Anthracene aoxidizes
Prepare anthraquinone H2O2System, which is put forth effort on, develops that catalytic activity and high stability while preparation process are simple, are easily isolated, valence
The cheap catalyst of lattice.
3, with O2Anthraquinone is prepared for oxidant
It is cheap relative to other raw materials since oxygen can detach acquisition directly from air, so oxygen is made
Carry out Oxidation Anthracene to prepare anthraquinone to be also a kind of current both economical method for oxidant.Spaniard Franeiseo is studied and is reported
A kind of simple and practicable method is led, which is made oxidant and obtained in laboratory scale using acetic aid medium, nitric acid, oxygen
Yield 80%, anthraquinone purity 99.6%.Experiment condition：28mg anthracenes, 125ml, 95% 0.075 liter/air of acetic acid control temperature 95
DEG C, reaction duration 2h.
But the strong oxidizing property and strong corrosive due to nitric acid damage seriously equipment etc., are unfavorable for its industrialization.When
Modern industrial circle pursue it is economical with it is environmentally protective, the state to maintain an equal level relatively is remain, in recent years, using oxygen as oxidant
Oxidation Anthracene prepares anthraquinone, and the catalyst mainly used has V2O5-TiO2、CuBr2、MnO2Deng.
Huang Zizheng etc. proposes a kind of face coat type catalyst, specially V2O5-TiO2Type catalyst, for being with oxygen
Oxidizer catalytic Oxidation Anthracene anthraquinone, while having investigated V2O5Influence with alkali metal content to the reaction is found with V2O5Contain
The yield of the increase of amount, the activity raising anthraquinone of catalyst reaches 95.3%, further increases V2O5Content, the deep oxidation of anthracene
The yield of aggravation, anthraquinone declines；Since alkali metal salt is added in catalyst so that catalyst activity reduction improves the choosing of anthraquinone
Selecting property selects suitable process conditions, the yield of anthraquinone that can reach 106.1%.
Zhang Yonghua finds, using aromatic halohydrocarbons and butyric acid mixed liquor as solvent, to be used as and urged by cobalt salt, manganese salt, bromide etc.
Agent, oxygen is as oxidant, and for control reaction pressure in 0.5-0.8MPa, it is 99.2% crystal anthracene that purity, which is made, in catalysis oxidation anthracene
Quinone, yield 93.7%, reaction solution can be used for multiple times by decoloration.
Cepeda etc. proposes a kind of using CuBr2Carry out the method that oxygen catalytic oxidation anthracene prepares anthraquinone, and studies and divide
The oxygen rates being passed through in liquid anthracene have been analysed, have been obtained in CuBr2The kinetic constant of oxygen is added under the induction of catalyst, and
It is 120-160 DEG C to be proposed optimal reaction temperature, and anthraquinone yield can reach 93.7%.Clark etc. [22] also proposed one kind
The method for using oxygen to prepare anthraquinone as oxidizing anthracene, using natural manganese oxide as catalyst, anthracene adds in air
The evaporation of Mn oxide slurries causes 30% anthracene to be oxidized to anthraquinone, natural manganese oxide ore substance can significantly improve oxygen with
The oxidation rate of anthracene, the anthracene of conversion 75% or so synthesize anthraquinone, and reaction is little with the relationship of temperature, and reaction condition is in room temperature
Under can carry out, but reaction rate is affected by pH, by experimental verification, in natural manganese oxide ore substance catalysis oxidation
Optimal pH is 4 or so during anthracene generates anthraquinone.Natural manganese oxide mineral plays an important role in pollutant decomposition, such as
PAHs pollutes problem common in urban soil.
By from existing document analysis it is found that by anthraquinone production method and applied analysis, showing that anthracene aoxidizes above
Method prepares anthraquinone with the advantages such as raw material abundance, relative inexpensiveness, environmental-friendly, is that anthraquinone ideal at present produces
Method.With industrially constantly increasing the demand of anthraquinone, suitable catalyst is selected to promote the effect that anthracene oxidation prepares anthraquinone
Rate is at one of current anthraquinone preparation field research hotspot.The environmental condition that dioxygen oxidation anthracene prepares anthraquinone is of less demanding, anthracene
Conversion ratio is relatively high, and the selectivity of anthraquinone is good, high income, and this method for preparing anthraquinone is generally applied to main life
The enterprise for producing anthraquinone, large-scale production, the pollution that anthraquinone may be implemented are few, and then improve the economic benefit of Chemical Manufacture.
Invention content
The purpose of the present invention is being directed to the method for providing anthracene oxidizing process in the prior art and preparing anthraquinone, for existing anthracene system
The reaction of standby anthraquinone, the activation energy needed are relatively high, it is necessary to it can just react at high temperature, and gas phase industrial at present is anti-
It answers, pollutes environment, drawback of high cost studies anthracene under low temperature and develops to the transformation of anthraquinone and prepare anthraquinone for anthracene oxidizing process
Catalyst is a kind of catalyst that can reduce the activation energy that anthracene is reacted to anthraquinone, converts at low temperature.
The method that anthracene oxidizing process prepares anthraquinone, includes the following steps：
1) saturated extent of adsorption of carrier is measured：Weigh carrier γ-Al2O3, distilled water is added dropwise to saturation, water used is
For the saturated extent of adsorption Vp of carrier；
2) with FeN3O9·9H2O、Zr(NO3)4·5H2O or FeN3O9·9H2O and Zr (NO3)4·5H2The mixture of O
It is mixed with single load or double supported catalysts for active component and carrier, is as follows：
With FeN3O9·9H2O is active component, and the amount concentration proportioning for preparing substance is：n(Fe)：N (Al)=0.02:1、
0.04:1、0.06:1、0.08:1、0.1:1 single supported catalyst；
With Zr (NO3)4·5H2O is active component, and the amount concentration proportioning for preparing substance is：n(Zr)：N (Al)=0.02:1、
0.04:1、0.06:1、0.08:1、0.1:1 single supported catalyst；
With FeN3O9·9H2O and Zr (NO3)4·5H2O is active component, and the amount concentration proportioning for preparing substance is：n(Fe)：n
(Zr)：N (Al)=0.02:0.02:1、0.04:0.04:1、0.06:0.06:1、0.08:0.08:1、0.1:0.1:1、0.02:
0.01:1、0.04:0.02:1、0.06:0.03:1、0.08:0.04:1、0.1:0.05:1 double supported catalysts；
3) normal temperature dipping, drying, roasting, taking-up cooling, obtain catalyst；
4) anthracene oxidation prepares anthraquinone：The catalyst that step 4) obtains is weighed, is added in anthracene reaction solution, is heated to 70 DEG C, stirs
It mixes, reacts, sampling, reaction was completed.
The saturated extent of adsorption of measurement carrier described in step 1) of the present invention, preferably weighs 5.00 grams of carrier γ-Al2O3, it is added dropwise
For distilled water to being saturated, water used (3.5ml) is the saturated extent of adsorption Vp (units of carrier：mL/g).
Normal temperature dipping, drying, roasting, taking-up cooling described in step 3), obtain catalyst, refer to normal temperature dipping 6-8h,
It is then placed in controlled at 120 DEG C of dry 6-7h in drying box, during which stirs 2-3 times, taken out by number successively after dried
It is put into crucible and covers, setting Muffle furnace calcination temperature program segment is room temperature → 200 DEG C 2h → 400 DEG C 2h → 600 DEG C 2h → 600
DEG C 6h → 300 DEG C 2h → 0 DEG C 1h finally takes out cooling, obtains catalyst.
Anthracene oxidation described in step 4) prepares anthraquinone：The catalyst that step 4) obtains is weighed, reaction solution (anthracene and equal three is added
Toluene mixture liquid), according to quality：Volume=0.5:20 ratio, anthracene reaction solution, preferably 50% mass concentration, is heated to 70 DEG C,
Mixing speed 20r/min starts to take first sample, second sample is taken after 3h, reaction was completed after stirring 1.5h.
Compared with prior art, the present invention has the following advantages：
1, since anthracene prepares the reaction of anthraquinone, the activation energy needed is relatively high, it is necessary to can just react at high temperature, at present
Industrial gas phase reaction pollutes environment, and of high cost, the catalyst that the present invention obtains is the work that can be reduced anthracene and be reacted to anthraquinone
The catalyst for changing energy, can realize transformation of the anthracene to anthraquinone under normal pressure, low temperature.
2, due to γ-Al2O3Aperture is bigger, is suitble to do the carrier of macromolecular reaction, and transition metal oxide active is high,
It is the investigation system of this paper experimental selections carrier and active component.
3, since compared to traditional synthetic method, oxidizing process, which prepares anthraquinone, to be had：Raw material is sufficient, cost is relatively inexpensive, ring
The advantages such as border close friend.
4, oxidizing process prepares the oxidant used by anthraquinone such as TPHB, H2O2、O2Deng various and be easy to synthetic method
It prepares, yield is high, wherein O2It is at low cost from air, it is environmentally protective.
Description of the drawings
Fig. 1 is the XRD spectra of sample a1, a2, a4 under the conditions of different Fe/Al ratios.
Fig. 2 is the XRD spectra of sample b1, b2, b4 under the conditions of different Zr/Al ratios.
Fig. 3 is the XRD spectra of sample c1, c2, c4 under the conditions of different Fe-Zr/Al ratios.
Specific implementation mode
The method for preparing anthraquinone to anthracene oxidizing process of the present invention by the following examples is described in further detail.But these
Embodiment is not regarded as limiting of the invention.
Embodiment：
1、γ-Al2O3The measurement of adsorbance
Equi-volume impregnating needs to measure the saturated extent of adsorption of carrier before preparing loaded catalyst.Method is as follows：Then claim
Take 5.00 grams of carrier γ-Al2O3, distilled water is added dropwise to being saturated, water used (3.5ml) is the saturated extent of adsorption Vp of carrier
(unit：mL/g).
2, different component catalyst preparation
With FeN3O9·9H2O is active component, wherein the amount concentration proportioning (table 3) for preparing substance is：n(Fe)：N (Al)=
0.02:1、0.04:1、0.06:1、0.08:1、0.1:1 five kinds of single supported catalysts.Five kinds of points of active components and carrier are mixed
Liquid is numbered and is sealed with preservative film respectively, and the sample impregnated is put into drying box controlled at 120 by normal temperature dipping 6-8h
DEG C dry 6-7h, process needs stirring 2-3 time, then dried sample is taken out to be sequentially placed into crucible by number and is covered, if
It is room temperature → 200 DEG C (2h) → 400 DEG C (2h) → 600 DEG C (2h) → 600 DEG C (6h) → 300 to set Muffle furnace calcination temperature program segment
DEG C (2h) → 0 DEG C (1h) finally takes out cooling, as anti-applications catalyst.
With Zr (NO3)4·5H2O is active component, wherein the amount concentration proportioning (table 3) for preparing substance is：n(Zr)：n(Al)
=0.02:1、0.04:1、0.06:1、0.08:1、0.1:1 five kinds of single supported catalysts.Five kinds of points of active components and carrier are mixed
Close liquid number and sealed with preservative film respectively, normal temperature dipping 6-8h, by the sample impregnated be put into drying box controlled at
120 DEG C of dry 6-7h, process needs stirring 2-3 times, then dried sample taking-up is sequentially placed into crucible by number and is covered,
Be arranged Muffle furnace calcination temperature program segment be room temperature → 200 DEG C (2h) → 400 DEG C (2h) → 600 DEG C (2h) → 600 DEG C (6h) →
300 DEG C (2h) → 0 DEG C (1h) finally takes out cooling, as anti-applications catalyst.
With FeN3O9·9H2O and Zr (NO3)4·5H2O is active component, wherein preparing a series of substance withdrawl syndrome proportionings
(table 4) is：n(Fe)：n(Zr)：N (Al)=0.02:0.02:1、0.04:0.04:1、0.06:0.06:1、0.08:0.08:1、
0.1:0.1:1、0.02:0.01:1、0.04:0.02:1、0.06:0.03:1、0.08:0.04:1、0.1:0.05:1 double loads
Catalyst.The sample impregnated is put into drying box controlled at 120 DEG C of dry 6h by normal temperature dipping 15h, and process needs stir
It mixes 2-3 times, then dried sample taking-up is once put into crucible by number and is covered, Muffle furnace calcination temperature program segment is set
For room temperature → 200 DEG C (2h) → 400 DEG C (2h) → 600 DEG C (2h) → 600 DEG C (6h) → 300 DEG C (2h) → 0 DEG C (1h), finally take
It is ground after going out cooling, as anti-applications catalyst.
3, anthracene oxidation prepares the reaction of anthraquinone and is carried out in three-necked flask, use heat collecting type constant-temperature heating magnetic stirring apparatus for
The detailed process of reaction unit, experiment is as follows：
1) water bath with thermostatic control is adjusted to 70 DEG C, weighs 0.5 gram of preparing catalyst, measures the reaction solution that 20ml has been prepared with pipette
(50%), it sequentially adds in three-necked flask, magnetite is added；
2) magnetic agitation is adjusted to 20r/min, and catalyst is made to be come into full contact with reaction solution, and simultaneous reactions liquid temperature is slowly increased to
70 DEG C or so.Start to take first sample after stirring 1.5h, second sample is taken after 3h, stops experiment.
Experimental example
Experiment is with γ-Al2O3For carrier, Fe, Zr oxide are active component, and Fe- γ-are prepared using equi-volume impregnating
Al2O3、Zr-γ-Al2O3Single supported catalyst and Fe-Zr/ γ-Al2O3Double supported catalysts.Investigate different activities catalytic
The structure of agent is to normal pressure, the influence of anthraquinone yield under low temperature, analyzes product using Ultra Performance Liquid Chromatography instrument, and aoxidize and close in anthracene
The catalytic performance of catalyst is evaluated in being reacted at anthraquinone, crystal situation in catalyst is analyzed by XRD characterization.
Experiment reagent and instrument
1 major experimental reagent of table
2 major experimental instrument of table
The mono- load active component proportionings of 3 Fe/Al, Zr/Al of table
The bis- load active component proportionings of 4 Fe-Zr/Al of table
3.1 catalyst characterization
3.1.1X x ray diffraction analysis x (XRD)
Analysis measurement, setting condition parameter are mutually carried out to catalyst object using X-ray diffractometer：Cu, Ka target, voltage
40kv, electric current 40mA, 2 θ scanning ranges are 10-50 °, scan residence time 0.5s, and the scanning number of degrees are 0.02 °.
The calcination temperature of each catalyst is 600 DEG C in Fig. 1, roasts 6h.A2 curves are Fe:Al=0.04:1 catalyst
XRD spectra, can obtain No. PDF is：89-8104 knows there is Fe by card number2O3It generates, Fe2O3It is respectively in 2 θ values
24.213 °, 33.255 °, 35.722 °, 40.973 °, 49.602 ° have diffraction maximum appearance, respectively corresponding (012), (104),
(110), (113), (024) crystal face.A4 curves are Fe:Al=0.08:1 catalyst XRD diagram, Fe2O3(PDF：89-8103) 2
θ values, which are respectively 24.216 °, 35.740 °, 39.373 °, 40.980 °, 43.640 °, diffraction maximum appearance, respectively corresponding (012),
(110), (006), (113), (202) crystal face.By comparing a1, a2, a4 XRD spectra it can be found that with Fe/Al than increasing
Greatly, the relative intensity of a4 diffraction maximums becomes larger, and shows that the load capacity for improving active component Fe is conducive to Fe2O3The formation of crystal,
But decline as the load capacity of active component increases anthraquinone yield.
The calcination temperature of each catalyst is 600 DEG C in Fig. 2, roasts 6h.B2 curves are Zr:Al=0.04:1 catalyst
XRD spectra, can obtain No. PDF is：14-0534 knows there is ZrO by card number2It generates, ZrO2It is respectively in 2 θ values
30.283 °, 34.487 °, 35.279 ° have diffraction maximum appearance, respectively corresponding (111), (002), (200) crystal face.B4 curves are Zr:
Al=0.08:1 catalyst XRD diagram, ZrO2(PDF：13-0307) 2 θ values be respectively 24.099 °, 28.245 °, 31.544 °,
34.236 °, 49.355 ° have diffraction maximum appearance, respectively corresponding (011), (- 111), (111), (002), (022) crystal face.Pass through ratio
XRD spectra compared with b1, b2, b4 it can be found that with Zr/Al than increase, the peak of b4 is relatively sharp, shows to improve active component
The load capacity of Zr is conducive to ZrO2The formation of crystal, but decline as the load capacity of active component increases anthraquinone yield.
The calcination temperature of each catalyst is 600 DEG C in Fig. 3, roasts 6h.C1 curves are Fe：Zr：Al=0.02:0.02:1
Catalyst XRD diagram, can obtain No. PDF is：02-1047,17-0559 know there is Fe by card number2O3、ZrO2It generates, c2
Curve is Fe:Zr:Al=0.04:0.04:1 catalyst XRD diagram, can obtain No. PDF is：89-8031,81-1544, by this
Card number knows there is Fe2O3、ZrO2It generates, Fe2O32 θ values and corresponding crystal face be respectively 24.216 ° (012), 33.243 °
(104), 49.607 ° (024), have diffraction maximum appearance, ZrO22 θ values and corresponding crystal face be respectively 30.283 ° (111),
34.487 ° (002) 35.279 ° (200), have diffraction maximum appearance.C4 curves are Fe:Zr:Al=0.08:0.08:1 catalyst
XRD diagram, can obtain No. PDF is：89-0599 knows there is Fe by card number203It generates, Fe2O3In 2 θ values and corresponding
Crystal face, which is respectively 24.169 ° (012), 33.193 ° (104), 35.656 ° (110), 40.896 ° (113), 49.506 ° (024), to be had
Diffraction maximum occurs.By comparing c1, c2, c4, XRD spectra it can be found that it is double load component of iron active component with load
The increase of amount, it is relatively apparent containing characteristic peak, but contain simultaneously with regard to more miscellaneous peaks, the amount that can be supported for zirconium active component is few, special
Levy peak unobvious.
The catalytic performance of 3.2 catalyst
The sample that anthracene oxidizing process is prepared to anthraquinone is overanxious with 0.25 micron of filtering head, bottling, and efficient using U3000 types
Liquid-phase chromatographic analysis anthracene oxidation product, test basis GB/T23495-2009,0.25 microlitre of each input.
3.3 interpretation of result
1, external standard method is established
(1) configuration 0.5g/L, 1g/L, 2g/L anthraquinone standard sample solution is built using the content of liquid chromatogram measuring anthraquinone
Vertical external standard curve.
(2) 1g/L, 5g/L, 10g/L anthracene standard sample solution are configured, using the content of liquid chromatogram measuring anthracene, is established outer
Mark song line.
(3) by external standard method detect different catalysts and the anthraquinone under different sample time (1.5h, 3h) content and
The surplus of anthracene calculates the conversion ratio of anthracene, the selectivity of anthraquinone, the yield etc. of anthraquinone by formula.Experimental result such as table
5.1。
5.1 different catalysts of table and reaction experiment result list
2, different catalyst component Comparative result analyses
The mono- supported catalysts of 5.2 Fe/Al, Zr/Al of table catalyze and synthesize the comparison of anthraquinone
As can be seen that a1, a2, a4, a5, b1, b2, b4, b5 corresponding are to be with Fe, Zr oxide from table 5.2
Single supported catalyst of active component, in the synthesis anthraquinone reaction of catalyst anthracene, the selectivity of anthraquinone reaches 100%, instead
Influence between seasonable to yield：React high income of the yield of 3h than reacting 1.5h anthraquinones；The active component of load is to yield
It influences：In the case where the identical proportioning temperature of different activities component is 70 DEG C, second sample analysis, conversion ratio and receipts are taken with 3h
Rate a1, a2, a4, a5 than b1, b2, b4, b5 high, can tentatively release Fe- γ-Al2O3Single supported catalyst ratio Zr- γ-
Al2O3Single supported catalyst activity is high, and anthraquinone yield is up to 2.6%, and corresponding is a2 catalyst.
The mono- loads of 5.3 Fe of table catalyze and synthesize the comparison of anthraquinone with the bis- supported catalysts of Fe-Zr
As can be seen that a1, a2, a4, a5 from table 5.3, it be with Fe oxides is activity that c1, c2, c4, c5 are corresponding
The single supported catalyst and Fe-Zr oxides of component are double supported catalysts of active component, in catalyst anthracene elbs reaction
In quinone reaction, the selectivity of anthraquinone reaches 100%, the influence of reaction time on yield：The yield of 3h is reacted than reaction 1.5h anthracenes
The high income of quinone；Influence of the active component of load to yield：In the identical proportioning of different loads active component, temperature is 70 DEG C
In the case of, second sample analysis is taken with 3h, conversion ratio and yield c1, c2, c4, c5 are than a1, a2, a4, a5 high.It can tentatively push away
Go out Fe-Zr/ γ-Al2O3Double supported catalyst ratio Fe- γ-Al2O3Single supported catalyst activity is high, and anthraquinone yield is up to
3.34%, corresponding is c2 catalyst.
The mono- loads of 5.4 Zr of table catalyze and synthesize the comparison of anthraquinone with the bis- supported catalysts of Fe-Zr
As can be seen that b1, b2, b4, b5 from table 5.4, it be with Zr oxides is activity that c1, c2, c4, c5 are corresponding
The single supported catalyst and Fe-Zr oxides of component are double supported catalysts of active component, in catalyst anthracene elbs reaction
In quinone reaction, the selectivity of anthraquinone reaches 100%, the influence of reaction time on yield：The yield of 3h is reacted than reaction 1.5h anthracenes
The high income of quinone；Influence of the active component of load to yield：In the identical proportioning of different loads active component, temperature is 70 DEG C
In the case of, second sample analysis is taken with 3h, conversion ratio and yield c1, c2, c4, c5 are than b1, b2, b4, b5 high.It can tentatively push away
Go out Fe-Zr/ γ-Al2O3Double supported catalyst ratio Zr- γ-Al2O3Single supported catalyst activity is high, and anthraquinone yield is up to
3.34%, corresponding is c2 catalyst.
Embodiment
6.1 Fe/ γ-Al of table2O3The specific surface area and pore volume of catalyst
| Catalyst forms | Calcination temperature/DEG C | SBET/(m2.g1) | Vtotal/(cm3.g1) |
| n(Fe)：N (Al)=0.02:1 | 600 | 137.5 | 0.28 |
| n(Fe)：N (Al)=0.04:1 | 600 | 179.2 | 0.37 |
| n(Fe)：N (Al)=0.06:1 | 600 | 176.7 | 0.32 |
| n(Fe)：N (Al)=0.08:1 | 600 | 174.1 | 0.30 |
| n(Fe)：N (Al)=0.1:1 | 600 | 177.5 | 0.37 |
6.2 Fe-Zr/ γ-Al of table2O3The specific surface area and pore volume of catalyst
| Catalyst forms | Calcination temperature/DEG C | SBET/(m2.g1) | Vtotal/(cm3.g1) |
| n(Fe)：N (Al)=0.02:1 | 600 | 147.3 | 0.33 |
| n(Fe)：N (Al)=0.04:1 | 600 | 180.1 | 0.38 |
| n(Fe)：N (Al)=0.06:1 | 600 | 156.7 | 0.35 |
| n(Fe)：N (Al)=0.08:1 | 600 | 144.1 | 0.32 |
| n(Fe)：N (Al)=0.1:1 | 600 | 149.5 | 0.34 |
Experimental studies results show：
1, under conditions of normal pressure, low temperature (70 DEG C), realize that anthracene catalysis oxidation prepares anthraquinone.Wherein, different type is urged
Agent has carried out catalytic performance and has compared, and the suitable catalyst for therefrom filtering out the synthesis anthraquinone reaction of catalysis oxidation anthracene is Fe-Zr/
γ-Al2O3(c2) double supported catalysts, reaction condition：70 DEG C of normal pressure, reaction temperature react 3h, Fe：Zr：Al=0.04:
0.04:When 1, the conversion ratio of anthracene is 3.34%, and for anthraquinone high selectivity up to 100%, anthraquinone yield is 3.34%.
2, according to XRD analysis, the catalyst Fe-Zr/ γ-Al of catalysis oxidation anthracene synthesis anthraquinone reaction are most suitable for2O3(c2),
Wherein activated centre may be the strongest Fe of diffraction maximum2O3、ZrO2Crystal, Fe2O32 θ values be respectively 24.216 °, 35.740 °,
39.373 °, 40.980 °, 43.640 ° have diffraction maximum appearance, and corresponding (012), (110), (006), (113), (202) are brilliant respectively
Face.ZrO2Being respectively 30.283 °, 34.487 °, 35.279 ° in 2 θ values has diffraction maximum appearance, respectively corresponding (111), (002),
(200) crystal face.
3, relatively more double load Fe-Zr/ γ-Al2O3With single load Fe- γ-Al2O3、Zr-γ-Al2O3Catalyst is observed
Double supported catalyst catalytic performances are preferable.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
It should all belong to the scope of protection of the present invention.
Claims (3)
1. the method that anthracene oxidizing process prepares anthraquinone, it is characterised in that：Include the following steps：
1) saturated extent of adsorption of carrier is measured：Weigh carrier γ-Al2O3, distilled water is added dropwise to being saturated, water used is to carry
The saturated extent of adsorption Vp of body；
2) with FeN3O9·9H2O、Zr(NO3)4·5H2O or FeN3O9·9H2O and Zr (NO3)4·5H2The mixture of O is to live
Property component and carrier be mixed with single load or double supported catalysts, be：
With FeN3O9·9H2O is active component, and the amount concentration proportioning for preparing substance is：n(Fe)：N (Al)=0.02:1、0.04:
1、0.06:1、0.08:1、0.1:1 single supported catalyst；
With Zr (NO3)4·5H2O is active component, and the amount concentration proportioning for preparing substance is：n(Zr)：N (Al)=0.02:1、
0.04:1、0.06:1、0.08:1、0.1:1 single supported catalyst；
With FeN3O9·9H2O and Zr (NO3)4·5H2O is active component, and the amount concentration proportioning for preparing substance is：n(Fe)：n
(Zr)：N (Al)=0.02:0.02:1、0.04:0.04:1、0.06:0.06:1、0.08:0.08:1、0.1:0.1:1、0.02:
0.01:1、0.04:0.02:1、0.06:0.03:1、0.08:0.04:1、0.1:0.05:1 double supported catalysts；
3) normal temperature dipping, drying, roasting, taking-up cooling, obtain catalyst；
4) anthracene oxidation prepares anthraquinone：The catalyst that step 4) obtains is weighed, is added in anthracene reaction solution, is heated to 70 DEG C, is stirred, instead
It answers, samples, reaction was completed.
2. the method that anthracene oxidizing process according to claim 1 prepares anthraquinone, it is characterised in that：Room temperature leaching described in step 3)
Stain, roasting, takes out cooling at drying, obtains catalyst, refers to normal temperature dipping 6-8h, be then placed in drying box controlled at
During which 120 DEG C of dry 6-7h are stirred 2-3 times, dried rear taking-up is sequentially placed into crucible by number to be covered, and setting Muffle furnace roasts
Burning temperature program(me) section is room temperature → 200 DEG C 2h → 400 DEG C 2h → 600 DEG C 2h → 600 DEG C 6h → 300 DEG C 2h → 0 DEG C 1h, is finally taken
Go out cooling, obtains catalyst.
3. the method that anthracene oxidizing process according to claim 1 prepares anthraquinone, it is characterised in that：Anthracene oxidation described in step 4)
Anthraquinone is prepared, is the catalyst for weighing step 4) and obtaining, is added in anthracene reaction solution, according to quality：Volume=0.5:20 ratio,
Anthracene reaction solution is 50% mass concentration, is heated to 70 DEG C, mixing speed 20r/min, starts to take first sample, 3h after stirring 1.5h
After take second sample, reaction was completed.
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