CN107812531A - A kind of olefinic unsaturated alcohol prepares the catalyst of alkene unsaturated aldehyde, Its Preparation Method And Use - Google Patents
A kind of olefinic unsaturated alcohol prepares the catalyst of alkene unsaturated aldehyde, Its Preparation Method And Use Download PDFInfo
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- CN107812531A CN107812531A CN201710979908.5A CN201710979908A CN107812531A CN 107812531 A CN107812531 A CN 107812531A CN 201710979908 A CN201710979908 A CN 201710979908A CN 107812531 A CN107812531 A CN 107812531A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- C07C45/37—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 >C—O—functional groups to >C=O groups
- C07C45/38—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 >C—O—functional groups to >C=O groups being a primary hydroxyl group
Abstract
The invention discloses a kind of olefinic unsaturated alcohol to prepare the catalyst of alkene unsaturated aldehyde, Its Preparation Method And Use.Described catalyst includes 1 30wt% silver, 0.1 10wt% copper, 0.01 1wt% rhenium, 0.01 1wt% molybdenum, 30 50wt% TiO2, 20 40wt% Ir5(PO4)6(OH)2.The catalyst aoxidizes especially suitable for the alcohol of 3 methyl, 2 butylene 1 prepares the aldehyde of 3 methyl, 2 butylene 1.The catalyst of the present invention has the features such as reactivity is high, and high temperature sintering resistant performance is strong, and stability is good, is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the catalyst that a kind of olefinic unsaturated alcohol prepares alkene unsaturated aldehyde, particularly 3- methyl -2- fourths
The oxidation of the alcohol of alkene -1 prepares catalyst of 3- methyl-2-butene -1- aldehyde and preparation method thereof.
Background technology
3- methyl-2-butene -1- aldehyde, also known as isoamyl olefine aldehydr, it is the raw material for synthesizing different vegetable alcohol；Starting can also be used as
Material synthesis citral, and then produce VitAVitE, beta carotene；It can be also used for synthesizing damascenone, irone
Deng spices.
Reported in patent JPS60246340 using silver and the copper composite catalyst being supported on carrier, at 400-500 DEG C
Under, 3-M2BOL is oxidized by oxygen obtained 3- methyl-2-butenes -1- aldehyde, and target product selectivity is up to 96%.
The reaction is needed to carry out under higher temperature conditionss, and catalyst is easily sintered in reaction continuous operation, reduces catalysis
The service life of agent.
3-M2BOL is reported in patent DE2715209 under oxygen atmosphere, using silver/copper crystal as catalysis
Agent carries out the process of oxidative dehydrogenation.Only have described in patent in silver catalyst particle diameter distribution is than more uniform or layer structure
Activity higher catalyst can just be obtained by having during certain particle diameter distribution, repeatability of such catalyst in actual production is very
Difference.Meanwhile reaction is also required under the hot conditions more than 300 DEG C to carry out, and equally exists catalyst easy-sintering, using the longevity
Order the problems such as short.
Reported in patent DE2517859 using tubular reactor under 150-300 DEG C, excessive oxygen atmosphere, copper catalysis
3-M2BOL synthesis 3- methyl-2-butene -1- aldehyde is aoxidized, although this catalyst not easy-sintering, course of reaction
The accessory substance of middle generation is more, and the selectivity of 3- methyl-2-butene -1- aldehyde is poor.
By above-mentioned patent it can be found that the simple metal of the composition such as noble silver, copper and corresponding loaded catalyst quilt
It is considered that unsaturated alcohol carries out the good catalysis of gas phase oxidation dehydrogenation reaction generation aldehydes or ketones using air or oxygen as oxidant
Agent.Have many patents and document report catalytic performance of such catalyst to unsaturated alcohol oxidative dehydrogenation, but this
A little metallic catalysts there is it is respective the shortcomings that.Copper catalyst is poor to unsaturated alcohol oxidation activity, and selectivity is very low,
Industrialized requirement can not be realized；Though silver catalyst is preferable to unsaturated alcohol oxidation activity, there are higher yield and selection
Property, but under the high temperature conditions, Nano silver grain easily agglomeration so that silver catalysis is easy to sinter, and causes the catalyst longevity
Life is shorter.Meanwhile the easy carbon distribution in catalyst surface in sintering process, cause catalyst duct to block, make reactor internal pressure
Rise, produce process safety problem.Therefore, develop a kind of catalyst for having both high activity and strong anti-sintering property and seem and particularly must
Will.
The content of the invention
It is an object of the invention to provide a kind of olefinic unsaturated alcohol to prepare alkene unsaturated aldehyde, particularly 3- methyl -2-
Butene-1-ol aoxidizes the support type composite metal catalyst for preparing 3- methyl-2-butene -1- aldehyde.The catalyst has high activity concurrently
With high temperature anti-sintering property.
It is another object of the present invention to provide the preparation method of the support type composite metal catalyst, the preparation side
Method technique is simple, cost is cheap.
To achieve the above objectives, technical scheme is as follows：
A kind of olefinic unsaturated alcohol prepares the support type composite metal catalyst of alkene unsaturated aldehyde, with overall catalyst weight
Meter, catalyst include：
Preferably, in terms of overall catalyst weight, catalyst includes：
In the present invention, described overall catalyst weight refers to the weight of final obtained catalyst prod.
In the present invention, the auxiliary agent such as rhenium element, molybdenum element can be effectively improved the reactivity worth of catalyst.
In the present invention, the carrier of catalyst is Ir5(PO4)6(OH)2And TiO2The compound formed, this compound load
In body, Ir5(PO4)6(OH)2Main stabilization Nano silver grain size acts on, and catalyst is had high temperature anti-sintering property, TiO2
Main stabilization catalytic structure acts on, and catalyst is had more preferable stability under the high temperature conditions.
The present invention also provides a kind of method for preparing described catalyst, comprises the steps of：Proportionally,
(1) to TiO2Ammoniacal liquor suspension in add Ir5(PO4)6(OH)2, at 40~100 DEG C, preferably 50~90 DEG C of conditions
Lower stirring 1~8h, preferably 3~6h, are stored at room temperature 8~14h of aging, preferably 10~12h, and obtained pelleting centrifugation is washed, cold
It is lyophilized it is dry after at 100~800 DEG C, 3~8h is calcined at preferably 200~600 DEG C, preferably 4~6h, it is standby to obtain carrier；
(2) after soluble silver salt solution is precipitated with precipitating reagent, add amine aqueous solution and dissolved to form silver-amine aqueous solution；
(3) soluble copper salt, soluble rhenium salt, soluble molybdenum salt are added in silver-amine aqueous solution of step (2) and mixed
Liquid；
(4) with carrier prepared in the mixed liquor spraying of gained in step (3) or impregnation steps (1), then done
It is dry, roasting, obtain catalyst.
TiO in step (1) of the present invention2Mass ratio with ammonia in ammoniacal liquor is 0.2~2.0: 1, preferably 0.5~1.5: 1.
The concentration of ammoniacal liquor in step (1) of the present invention is 10~50wt%, preferably 20~30wt%.
Precipitating reagent in step (2) of the present invention is selected from ammonium oxalate and/or ammonium carbonate, preferably ammonium oxalate.The precipitation
The mol ratio of agent and the silver element in soluble silver salt is 1.25~2: 1, preferably 1.5~1.7: 1.The precipitating reagent preferably with
The form of solution uses, and the concentration of the solution is 0.1~25mol/L, preferably 1~10mol/L；The solvent of the solution is preferred
Water.
The amine of amine aqueous solution described in step (2) of the present invention is selected from ethylenediamine and/or the third triamine, preferably ethylenediamine.
The mol ratio of amine and the silver element in soluble silver salt is 1.2~3: 1, preferably 1.5~2: 1 in the amine aqueous solution.Described amine
The concentration of solution is 0.1~15mol/L.The preferred water of solvent of the amine aqueous solution.
One or more of the soluble silver salt of the present invention in silver fluoride, silver perchlorate, silver nitrate, preferably nitre
Sour silver.The concentration of soluble silver salt solution is 0.1~50mol/L, preferably 1~20mol/L.The soluble silver salt solution it is molten
The preferred water of agent.
One or more of the soluble copper salt of the present invention in copper nitrate, copper chloride, copper sulphate, preferably nitric acid
Copper.
Soluble rhenium salt of the present invention is the one or more in nitric acid rhenium, sulfuric acid rhenium, carbonic acid rhenium, preferably nitric acid
Rhenium.
Soluble molybdenum salt of the present invention is the one or more in nitric acid molybdenum, molybdenum trisulfate, carbonic acid molybdenum, preferably nitric acid
Molybdenum.
Drying in step (4) of the present invention can be carried out in air or inert gas atmosphere, and drying temperature is
50~120 DEG C, preferably 60~100 DEG C.
The temperature of roasting in step (4) of the present invention be 200~600 DEG C, preferably 300~450 DEG C, the gas of roasting
Atmosphere can be air, nitrogen etc..The time of roasting is 0.1~3h, preferably 0.5~1h.
The catalyst of the present invention prepares 3- methyl -2- fourths especially suitable for 3-M2BOL gas phase oxidation
Alkene -1- aldehyde, the reaction comprise the following steps：Unstripped gas under the catalysis of catalyst of the present invention, reaction temperature be 250~
450 DEG C, preferably 320~420 DEG C, air speed are 3000~40000h-1, preferably in 10000~25000h-1Reacted.The original
Expect in gas, the mol ratio of 3-M2BOL and oxygen is 1: 0.01~0.5, preferably 1: 0.2~0.4.Carrier gas can be with
It is any inert gas, preferably nitrogen.
Air speed of the present invention refers in the unit interval, under the standard state that per volume of catalyst passes through gas body
Product.
The reactor of gas phase oxidation of the present invention can use any reactor well known in the art, preferably tubular type
Reactor.
The catalyst of the present invention combines the advantages of silver and copper catalyst, simultaneously because the element auxiliary agent such as rhenium, molybdenum is added,
Make it have the characteristics of activity is high.Meanwhile Ir in carrier5(PO4)6(OH)2The size of Nano silver grain can be stablized, make catalysis
Agent possesses the anti-sintering characteristic of high temperature.In applied to 3-M2BOL oxidation reaction, 3-M2BOL
High conversion rate be up to 97~99% up to the selectivity of 70~75%, 3- methyl-2-butene -1- aldehyde, react in 4000 hours,
Catalyst activity is stable.The preparation method of the catalyst of the present invention is simple, and used raw material is cheap and easily-available, is suitable for extensive
Industrial applications.
Specific implementation method
Analytical conditions for gas chromatography：
Shimadzu GC-2014 on-line analyses gas-chromatography configures one ten logical high temperature sampling valve and two six-way valves, two hydrogen
Flame example detector (FID) and a thermal conductivity cell detector (TCD), using DB-17 chromatographic columns and FID detection reaction generations
Organic matter, 13X molecular sieve columns and damping column combination TCD and CO, CO2, O2, N2 of fid detector detection constant and trace etc..
Chromatographic column：Shimadzu DB-17 (specification is 50m × 0.32mm × 0.25mm)
Injector temperature：280℃
Split ratio：30∶1
Column flow：1.5ml/min
Chromatographic column heating schedule：50 DEG C of holdings 1min, 5 DEG C/min are increased to 280 DEG C
Hydrogen flowing quantity：35ml/min
Air mass flow：350ml/min.
Embodiment 1：
Catalyst A preparation：Under agitation 5.25g TiO are added into the ammoniacal liquor that 43.24g concentration is 25wt%2
Suspension is formed it into, 3.99g Ir is added into this suspension5(PO4)6(OH)2, 5h is reacted under the conditions of 60 DEG C, room temperature is quiet
Aging 11h is put, obtained pelleting centrifugation is washed, be calcined 5h under the conditions of through 400 DEG C after freeze-drying uses as carrier；Will
0.17g AgNO3 is dissolved in 0.2mL water, and 0.20g (NH4) 2C2O4 is dissolved in 0.32mL water, and two solution are placed in into 40 DEG C of water-baths
Reacted under middle stirring condition.Precipitation is washed after reacting 1h, washs and adds 0.34mL's in 2-3 this backward sediment
Silver-amine complex liquid is made in 5mol/L ethylenediamine solution, and 3.08gCu (NO are added into silver-amine complex liquid of gained3)2、
0.002gRe(NO3)3、0.38gMo(NO3)4Homogeneous solution is dissolved into, the carrier prepared is added into above-mentioned solution, is stirred
About 1h, solvent is steamed under the conditions of 100 DEG C, 0.7h is calcined under the conditions of 350 DEG C and obtains catalyst A 10.5g.Wherein, silver accounts for
1wt%, copper account for 10wt%, rhenium accounts for 0.01wt%, molybdenum accounts for 1wt%, TiO2Account for 50%, Ir5(PO4)6(OH)2Account for 37.99wt%.
Catalyst A reactivities are tested：By catalyst breakage to 30-60 mesh, 2ml is taken to load the reaction tube that internal diameter is 1cm
In, enter raw material 3-M2BOL 10g per hour, enter oxygen 0.9L, enter nitrogen 2.1L, set reacting initial temperature
350 DEG C, reaction focus is 375 DEG C, and gas chromatographic analysis reaction product obtains reaction conversion ratio 70%, 3- methyl-2-butenes-
1- aldehyde selectivity 98%.
Catalyst A service lifes are tested：Operate continuously under above-mentioned process conditions, per 4h sampling analyses, reacted in 4000h
Activity has no reduction, and conversion ratio is maintained at 69~72%, and reaction conversion ratio is opened after being selectively maintained at 97~98%, 4300 hours
Begin to reduce, until after 5000h, conversion ratio is down to less than 50%.
Embodiment 2：
Catalyst B preparation：Except using 3.06g AgNO3、2.16g Cu(NO3)2、0.01g Re(NO3)3、0.30g
Mo(NO3)4、3.68g TiO2、4.06g Ir5(PO4)6(OH)2, 3.57g (NH4) 2C2O4,6.12ml concentration be 5mol/L second
Outside two amine aqueous solutions, the ammoniacal liquor that 30.26g concentration is 25wt%, remaining is with reference to embodiment 1.In the catalyst B of gained, silver accounts for
18.50wt%, copper account for 7wt%, rhenium accounts for 0.05wt%, molybdenum accounts for 0.80wt%, TiO2Account for 35%, Ir5 (PO4)6(OH)2Account for
38.65wt%.
Catalyst B reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 72%, 3- methyl-
2- butene-1s-aldehyde selectivity 97%.
Catalyst B service lifes are tested：Tested with reference to the method for embodiment 1, reactivity has no drop in 4000h
Low, conversion ratio is maintained at 69~72%, and reaction conversion ratio starts to reduce after being selectively maintained at 97~98%, 4200 hours, directly
To 5000h, conversion ratio is down to less than 50%.
Embodiment 3：
Catalyst C preparation：Except using 4.13g AgNO3、0.15g Cu(NO3)2、0.09g Re(NO3)3、0.16g
Mo(NO3)4、4.20g TiO2、3.53g Ir5(PO4)6(OH)2, 4.82g (NH4) 2C2O4,8.27ml concentration be 5mol/L second
Outside two amine aqueous solutions, the ammoniacal liquor that 34.59g concentration is 25wt%, remaining is with reference to embodiment 1.In the catalyst C of gained, silver accounts for
25wt%, copper account for 0.5wt%, rhenium accounts for 0.43wt%, molybdenum accounts for 0.43wt%, TiO2Account for 40%, Ir5(PO4)6(OH)2Account for
33.65wt%.
Catalyst C reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 75%, 3- methyl-
2- butene-1s-aldehyde selectivity 99%.
Catalyst C service lifes are tested：Tested with reference to the method for embodiment 1, reactivity has no drop in 4000h
Low, conversion ratio is maintained at 73~75%, and reaction conversion ratio starts to reduce after being selectively maintained at 97~99%, 4100 hours, directly
To 5000h, conversion ratio is down to less than 50%.
Embodiment 4：
Catalyst D preparation：Except using 1.98g AgNO3、1.16g Cu(NO3)2、0.17g Re(NO3)3、0.02g
Mo(NO3)4、4.73g TiO2、4.03g Ir5(PO4)6(OH)2, 2.31g (NH4) 2C2O4,3.96ml concentration be 5mol/L second
Outside two amine aqueous solutions, the ammoniacal liquor that 38.91g concentration is 25wt%, remaining is with reference to embodiment 1.In the catalyst D of gained, silver accounts for
12wt%, copper account for 3.75wt%, rhenium accounts for 0.80wt%, molybdenum accounts for 0.05wt%, TiO2Account for 45%, Ir5(PO4)6(OH)2Account for
38.40wt%.
Catalyst D reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 70%, 3- methyl-
2- butene-1s-aldehyde selectivity 98%.
Catalyst D service lifes are tested：Tested with reference to the method for embodiment 1, reactivity has no drop in 4000h
Low, conversion ratio is maintained at 69~72%, and reaction conversion ratio starts to reduce after being selectively maintained at 97~98%, 4100 hours, directly
To 5000h, conversion ratio is down to less than 50%.
Embodiment 5：
Catalyst E preparation：Except using 4.96g AgNO3、0.03g Cu(NO3)2、0.21g Re(NO3)3、0.004g
Mo(NO3)4、3.15g TiO2、4.08g Ir5(PO4)6(OH)2, 5.79g (NH4) 2C2O4,9.93ml concentration be 5mol/L second
Outside two amine aqueous solutions, the ammoniacal liquor that 25.94g concentration is 25wt%, remaining is with reference to embodiment 1.In the catalyst E of gained, silver accounts for
30wt%, copper account for 0.10wt%, rhenium accounts for 1.0wt%, molybdenum accounts for 0.01wt%, TiO2Account for 30%, Ir5(PO4)6(OH)2Account for
38.89wt%.
Catalyst E reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 73%, 3- methyl-
2- butene-1s-aldehyde selectivity 97%.
Catalyst E service lifes are tested：Tested with reference to the method for embodiment 1, reactivity has no drop in 4000h
Low, conversion ratio is maintained at 70~73%, and reaction conversion ratio starts to reduce after being selectively maintained at 97~98%, 4300 hours, directly
To 5000h, conversion ratio is down to less than 50%.
Embodiment 6：
Catalyst F preparation：Except using 4.96g AgNO3、3.08g Cu(NO3)2、0.17g Re(NO3)3、0.02g
Mo(NO3)4、4.11g TiO2、2.10g Ir5(PO4)6(OH)2, 5.79g (NH4) 2C2O4,9.93ml concentration be 5mol/L second
Outside two amine aqueous solutions, the ammoniacal liquor that 33.85g concentration is 25wt%, remaining is with reference to embodiment 1.In the catalyst F of gained, silver accounts for
30wt%, copper account for 10wt%, rhenium accounts for 0.8wt%, molybdenum accounts for 0.05wt%, TiO2Account for 39.15%, Ir5(PO4)6(OH)2Account for
20wt%.
Catalyst F reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 74%, 3- methyl-
2- butene-1s-aldehyde selectivity 98%.
Catalyst F service lifes are tested：Tested with reference to the method for embodiment 1, reactivity has no drop in 4000h
Low, conversion ratio is maintained at 72~75%, and reaction conversion ratio starts to reduce after being selectively maintained at 97~98%, 4200 hours, directly
To 5000h, conversion ratio is down to less than 50%.
Embodiment 7：
Catalyst G preparation：Except using 4.96g AgNO3、1.16g Cu(NO3)2、0.17g Re(NO3)3、0.02g
Mo(NO3)4、4.24g TiO2、2.63g Ir5(PO4)6(OH)2, 5.79g (NH4) 2C2O4,9.93ml concentration be 5mol/L second
Outside two amine aqueous solutions, the ammoniacal liquor that 34.93g concentration is 25wt%, remaining is with reference to embodiment 1.In the catalyst G of gained, silver accounts for
30wt%, copper account for 3.75wt%, rhenium accounts for 0.8wt%, molybdenum accounts for 0.05wt%, TiO2Account for 40.40%, Ir5(PO4)6(OH)2Account for
25wt%.
Catalyst G reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 75%, 3- methyl-
2- butene-1s-aldehyde selectivity 97%.
Catalyst G service lifes are tested：Tested with reference to the method for embodiment 1, reactivity has no drop in 4000h
Low, conversion ratio is maintained at 72~75%, and reaction conversion ratio starts to reduce after being selectively maintained at 97~98%, 4100 hours, directly
To 5000h, conversion ratio is down to less than 50%.
Embodiment 8：
Catalyst H preparation：Except using 3.06g AgNO3、2.16g Cu(NO3)2、0.01g Re(NO3)3、0.30g
Mo(NO3)4、4.58g TiO2、3.15g Ir5(PO4)6(OH)2, 3.57g (NH4) 2C2O4,6.13ml concentration be 5mol/L second
Outside two amine aqueous solutions, the ammoniacal liquor that 37.74g concentration is 25wt%, remaining is with reference to embodiment 1.In the catalyst H of gained, silver accounts for
18.50wt%, copper account for 7wt%, rhenium accounts for 0.05wt%, molybdenum accounts for 0.80wt%, TiO2Account for 43.65%, Ir5(PO4)6(OH)2Account for
30wt%.
Catalyst H reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 70%, 3- methyl-
2- butene-1s-aldehyde selectivity 98%.
Catalyst H service lifes are tested：Tested with reference to the method for embodiment 1, reactivity has no drop in 4000h
Low, conversion ratio is maintained at 69~72%, and reaction conversion ratio starts to reduce after being selectively maintained at 97~98%, 4200 hours, directly
To 5000h, conversion ratio is down to less than 50%.
Embodiment 9：
Catalyst I preparation：Except using 1.98g AgNO3、3.08g Cu(NO3)2、0.002g Re(NO3)3、0.38g
Mo(NO3)4、4.41g TiO2、3.68g Ir5(PO4)6(OH)2, 2.31g (NH4) 2C2O4,3.96ml concentration be 5mol/L second
Outside two amine aqueous solutions, the ammoniacal liquor that 36.31g concentration is 25wt%, remaining is with reference to embodiment 1.In the catalyst I of gained, silver accounts for
12wt%, copper account for 10wt%, rhenium accounts for 0.01wt%, molybdenum accounts for 1wt%, TiO2Account for 41.99%, Ir5(PO4)6(OH)2Account for 35wt%.
Catalyst I reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 70%, 3- methyl-
2- butene-1s-aldehyde selectivity 97%.
Catalyst I service lifes are tested：Tested with reference to the method for embodiment 1, reactivity has no drop in 4000h
Low, conversion ratio is maintained at 69~72%, and reaction conversion ratio starts to reduce after being selectively maintained at 97~98%, 4200 hours, directly
To 5000h, conversion ratio is down to less than 50%.
Comparative example 1：
Catalyst J preparation：Except using 4.96g AgNO3、3.08g Cu(NO3)2、0.210g Re(NO3)3、0.38g
Mo(NO3)4、6.09g TiO2, 5.79g (NH4) 2C2O4,9.93ml concentration be 5mol/L ethylenediamine solution, 50.15g it is dense
Spend the ammoniacal liquor for 25wt%, without using Ir5(PO4)6(OH)2Outside, remaining is with reference to embodiment 1.In the catalyst J of gained, silver accounts for
30wt%, copper account for 10wt%, rhenium accounts for 1.0wt%, molybdenum accounts for 1.0wt%, TiO2Account for 58%.
Catalyst J reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 70%, 3- methyl-
2- butene-1s-aldehyde selectivity 97%.
Catalyst J service lifes are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio is opened after 1000 hours
Begin to reduce, until after 1500h, conversion ratio is down to less than 50%.
Comparative example 2：
Catalyst K preparation：Except using 1.98g AgNO3、1.16g Cu(NO3)2、4.73g TiO2、4.12g Ir5
(PO4)6(OH)2, 2.31g (NH4) 2C2O4,3.96ml concentration be 5mol/L ethylenediamine solution, 38.91g concentration be
25wt% ammoniacal liquor, without using Re (NO3)3With Mo (NO3)4Outside, remaining is with reference to embodiment 1.In the catalyst K of gained, silver accounts for
12wt%, copper account for 3.75wt%, TiO2Account for 45%, Ir5(PO4)6(OH)2Account for 39.25wt%.
Catalyst K reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 52%, 3- methyl-
2- butene-1s-aldehyde selectivity 70%.
Comparative example 3：
Catalyst L preparation：Except using 1.98g AgNO3、1.16g Cu(NO3)2、0.21g Re(NO3)3、4.73g
TiO2、4.02g Ir5(PO4)6(OH)2, 2.31g (NH4) 2C2O4,3.96ml concentration be 5mol/L ethylenediamine solution,
38.91g concentration is 25wt% ammoniacal liquor, without using Mo (NO3)4Outside, remaining is with reference to embodiment 1.In gained catalyst L, silver accounts for
12wt%, copper account for 3.75wt%, rhenium accounts for 1.0wt%, TiO2Account for 45%, Ir5(PO4)6(OH)2Account for 38.25wt%.
Catalyst L reactivities are tested：Tested with reference to the method for embodiment 1, reaction conversion ratio 60%, 3- methyl-
2- butene-1s-aldehyde selectivity 85%.
Claims (10)
1. a kind of olefinic unsaturated alcohol prepares the catalyst of alkene unsaturated aldehyde, it is characterised in that in terms of overall catalyst weight, catalysis
Agent includes：
Preferably, in terms of overall catalyst weight, catalyst includes：
2. a kind of preparation method of the catalyst described in claim 1, comprises the following steps：
(1) to TiO2Ammoniacal liquor suspension in add Ir5(PO4)6(OH)2, stirring, aging is stored at room temperature, obtained precipitation is washed
Wash, be freeze-dried, roasting, it is standby to obtain carrier；
(2) after soluble silver salt solution is precipitated with precipitating reagent, add amine aqueous solution and dissolved to form silver-amine aqueous solution；
(3) soluble copper salt, soluble rhenium salt, soluble molybdenum salt are added in silver-amine aqueous solution of step (2) and obtains mixed liquor；
(4) with carrier prepared in the mixed liquor spraying of gained in step (3) or impregnation steps (1), then it is dried, roasts
Burn, obtain catalyst.
3. according to the method for claim 2, it is characterised in that whipping temp is 40~100 DEG C in the step (1), excellent
Select 50~90 DEG C；Mixing time is 1~8h.
4. according to the method in claim 2 or 3, it is characterised in that the temperature of roasting is 100~800 in the step (1)
DEG C, preferably 200~600 DEG C；Roasting time is 3~8h, preferably 4~6h.
5. according to the method described in claim any one of 2-4, it is characterised in that described precipitating reagent is ammonium oxalate and/or carbon
Sour ammonium, preferably ammonium oxalate；The mol ratio of the precipitating reagent and the silver element in soluble silver salt is 1.25~2：1, preferably 1.5
~1.7：1.
6. according to the method described in claim any one of 2-5, it is characterised in that the amine in described amine aqueous solution is ethylenediamine
And/or third triamine；The mol ratio of the silver element in amine and soluble silver salt in the amine aqueous solution is 1.2~3：1, preferably 1.5
~2：1.
7. according to the method described in claim any one of 2-6, it is characterised in that described soluble silver salt be selected from silver fluoride,
One or more in silver perchlorate, silver nitrate；
The soluble copper salt in copper nitrate, copper chloride, copper sulphate any one or more；
Described soluble rhenium salt is one or more in nitric acid rhenium, sulfuric acid rhenium, carbonic acid rhenium；
Described soluble molybdenum salt is one or more in nitric acid molybdenum, molybdenum trisulfate, carbonic acid molybdenum.
8. according to the method described in claim any one of 2-7, it is characterised in that the drying temperature in the step (4) is 50
~120 DEG C, preferably 60~100 DEG C；The temperature of roasting in described step (4) is 200~600 DEG C, preferably 300~450 DEG C；
The time of roasting is 0.1~3h, preferably 0.5~1h.
9. a kind of method that the alcohol of 3- methyl-2-butenes -1 oxidation prepares 3- methyl-2-butene -1- aldehyde, comprises the following steps, uses
Catalyst prepared by the method described in the catalyst or claim any one of 2-7 described in claim 1,3- methyl-2-butenes-
1- alcohol is 250~450 DEG C in reaction temperature with oxygen, and preferably 320~420 DEG C, air speed is 3000~40000h-1, preferably exist
10000~25000h-1Reacted.
10. according to the method for claim 9, it is characterised in that mole of the 3-M2BOL and oxygen
Than for 1：0.01~0.5, preferably 1：0.2~0.4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110368938A (en) * | 2019-08-09 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of preparation method for 3-M2BOL synthesis isoamyl olefine aldehydr catalyst |
| CN111298808A (en) * | 2020-04-02 | 2020-06-19 | 万华化学集团股份有限公司 | Preparation method and application of core-shell catalyst |
| CN114534787A (en) * | 2020-11-24 | 2022-05-27 | 万华化学集团股份有限公司 | Isopentenol gas-phase dehydrogenation catalyst and method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422691A (en) * | 2002-10-24 | 2003-06-11 | 中国科学院兰州化学物理研究所 | Catalyst for preparing aldehyde by oxidation dehydrogenation of 3-methyl-butenol and preparation method thereof |
| CN101959837A (en) * | 2008-02-28 | 2011-01-26 | 巴斯夫欧洲公司 | Method for producing olefinically saturated carbonyl compounds by oxidative dehydrogenation of alcohols |
| CN101977684A (en) * | 2008-03-19 | 2011-02-16 | 巴斯夫欧洲公司 | Use of a supported catalyst containing precious metal for oxidative dehydrogenation |
| CN103769162A (en) * | 2012-10-24 | 2014-05-07 | 万华化学集团股份有限公司 | Loaded composite metal catalyst used for unsaturated alcohol oxidation and preparation method thereof |
| CN105080582A (en) * | 2014-05-07 | 2015-11-25 | 中国科学院大连化学物理研究所 | High-activity anti-sintering aurum catalyst and preparation therefor and application thereof |
-
2017
- 2017-10-19 CN CN201710979908.5A patent/CN107812531B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422691A (en) * | 2002-10-24 | 2003-06-11 | 中国科学院兰州化学物理研究所 | Catalyst for preparing aldehyde by oxidation dehydrogenation of 3-methyl-butenol and preparation method thereof |
| CN101959837A (en) * | 2008-02-28 | 2011-01-26 | 巴斯夫欧洲公司 | Method for producing olefinically saturated carbonyl compounds by oxidative dehydrogenation of alcohols |
| CN101977684A (en) * | 2008-03-19 | 2011-02-16 | 巴斯夫欧洲公司 | Use of a supported catalyst containing precious metal for oxidative dehydrogenation |
| CN103769162A (en) * | 2012-10-24 | 2014-05-07 | 万华化学集团股份有限公司 | Loaded composite metal catalyst used for unsaturated alcohol oxidation and preparation method thereof |
| CN105080582A (en) * | 2014-05-07 | 2015-11-25 | 中国科学院大连化学物理研究所 | High-activity anti-sintering aurum catalyst and preparation therefor and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110368938A (en) * | 2019-08-09 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of preparation method for 3-M2BOL synthesis isoamyl olefine aldehydr catalyst |
| CN110368938B (en) * | 2019-08-09 | 2022-02-11 | 中触媒新材料股份有限公司 | Preparation method of catalyst for synthesizing isopropenal from 3-methyl-2-butene-1-ol |
| CN111298808A (en) * | 2020-04-02 | 2020-06-19 | 万华化学集团股份有限公司 | Preparation method and application of core-shell catalyst |
| CN111298808B (en) * | 2020-04-02 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method and application of core-shell catalyst |
| CN114534787A (en) * | 2020-11-24 | 2022-05-27 | 万华化学集团股份有限公司 | Isopentenol gas-phase dehydrogenation catalyst and method |
| CN114534787B (en) * | 2020-11-24 | 2023-12-19 | 万华化学集团股份有限公司 | Gas-phase dehydrogenation catalyst and method for isopentenol |
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