CN103769162B - A kind of support type composite metal catalyst for unsaturated alcohol oxidation and preparation method thereof - Google Patents
A kind of support type composite metal catalyst for unsaturated alcohol oxidation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of support type composite metal catalyst for unsaturated alcohol oxidation and preparation method thereof, described catalyst comprises: the alkali metal of 0.001-0.3wt%, the alkaline-earth metal of 0.001-1wt%, the scandium element of 0.001-1wt%, the cerium oxide of 0.05-1wt% and zirconia sol, the copper of 0.3-10wt%, the silver of 1-30wt%, the carrier of 60-95wt%.Its preparation method is with after precipitating reagent precipitated silver salting liquid, the silver-colored sediment aminated compounds of gained is made silver-amine aqueous solution, the amine complex liquid of soluble copper salt, scandium salts, alkali metal salt, alkali salt and auxiliary agent and silver-amine aqueous solution are sprayed or impregnated catalyst support, obtains supported silver, copper composite catalyst through super-dry, roasting afterwards.The features such as it is high that catalyst of the present invention has reactivity, good stability, and the three wastes are few, are suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of support type composite metal catalyst for unsaturated alcohol oxidation and preparation method thereof.
Background technology
In organic synthesis, oxidation reaction is an important process, to functionalized the playing an important role of medicine, fine chemistry industry and chemurgy product reaction intermediate.No matter be laboratory preparation or suitability for industrialized production, in various types of oxidation conversion, oxidizing process alcohol being oxidized to carbonyls all occupies critical role.Chemically performance and in various uses, carbonyls occupies special critical positions, the beginning raw material that they synthesize often.This namely aldehyde, ketone become the chemical process particularly important source material of fine chemistry industry process and the reason of intermediate, therefore alcohol being oxidized to corresponding carbonyls is one of most important course of reaction in organic chemistry.Conventional oxidation method, needs on the one hand to use plurality of heavy metal reagent, adds cost of material; On the other hand, a large amount of discarded object severe contaminations environment that produces of course of reaction.The environmental pollution become increasingly conspicuous now is also one makes us stubborn problem, so how to address these problems more and more is subject to people's attention.Therefore no matter from the angle of economy, or the viewpoint of protection of the environment and sustainable development, in the urgent need to developing the dioxygen oxidation method of the green of high-efficiency cleaning.
For a long time, the simple metal of the composition such as noble metal gold, silver, copper and corresponding loaded catalyst are considered to unsaturated alcohol and make oxidant with air or oxygen and carry out the good catalyst that gas phase oxidation dehydrogenation reaction generates aldehydes or ketones.Have a lot of patents and the bibliographical information catalytic performance of such catalyst to unsaturated alcohol oxidative dehydrogenation, but these metallic catalysts all also exist respective shortcoming.Though silver catalyst is better to unsaturated alcohol oxidation activity, have higher yield and selective, under hot conditions, catalyst easily sinters gathering, thus catalyst life is shorter, needs continually more catalyst changeout, causes silver catalyst stable in fact not.And copper catalyst is poor to unsaturated alcohol oxidation activity, selective very low, industrialized requirement cannot be realized.Become by silver alloy to need to consume a large amount of man power and materials with copper weld pool, and operating process is loaded down with trivial details, implements difficulty larger.And although Au catalyst reactivity is fine, expensive, considerably increase the cost of production process.
3-methyl-2-butene aldehyde is a kind of important industrial chemicals, and it may be used for manufacturing dyestuff, pesticide, medicine, plastics, vitamin, spices etc.US2042220 teaches 3-methyl-2-butene aldehyde and can be obtained via metallic catalyst (as copper or silver catalyst) catalysis by 3-methyl-3-butenol and excessive oxygen mix, catalyst can be alloy, metallic compound or metallic element, and copper catalyst is obtained by reduction under copper oxide particulate 300 DEG C of hydrogen atmosphere.It is catalyst with metallic copper that patent DE-B2517859 describes 3-methyl-3-butenol under the condition that there is not oxygen, creates a large amount of formaldehyde by-product, significantly reduces several days inner catalysts are active, therefore haves no alternative but the frequent regeneration needing to carry out catalyst.
DE-B2715209 and EP-B55354 describes 3-methyl-3-butenol and carry out the process of oxidative dehydrogenation with silver or copper crystal for catalyst under oxygen existence condition, the shortcoming of this process is that catalyst costs is very high, only at silver catalyst domain size distribution relatively evenly or just can obtain when there is certain domain size distribution in layer structure, even need the particular combination of silver and copper catalyst in some example, therefore be not only reactor and handle costliness, catalyst is also difficult to repeat, in addition, higher reaction temperature used in this process can make sintering of catalyst, thus cause pressure increase.
BASF patent US5149884 and US6013843 is that catalyst adopts shell and tube reactor to carry out the reaction that 3-methyl-3-butenol is oxidized to 3-methyl-2-butene aldehyde with fine silver granules, and conversion ratio can reach 52-55%, selective 90-92%.
In view of the various problems that unsaturated alcohol oxidation reaction catalyst exists, in the urgent need to developing the high and stable catalyst of new activity.
Summary of the invention
The object of the present invention is to provide a kind of support type composite metal catalyst for unsaturated alcohol oxidation, catalyst of the present invention combines the advantage of existing copper, silver catalyst, and the active and more existing catalyst of stability is greatly improved.
Another object of the present invention is the preparation method of the support type composite metal catalyst being provided for unsaturated alcohol oxidation, and this preparation technology is simple, cost is low.
3rd object of the present invention is to provide above-mentioned catalyst to generate the application of carbonyls in unsaturated alcohol oxidation reaction.
For reaching above object, technical scheme of the present invention is as follows:
For a support type composite metal catalyst for unsaturated alcohol oxidation, in overall catalyst weight, catalyst comprises:
(1) alkali metal of 0.001-0.3wt%
(2) alkaline-earth metal of 0.001-1wt%
(3) scandium of 0.001-1wt%
(4) cerium oxide of 0.05-1wt% and zirconia sol
(5) copper of 0.3-10wt%
(6) silver of 1-30wt%
(7) carrier of 60-95wt%
As preferred scheme, in overall catalyst weight, catalyst comprises:
(1) alkali metal of 0.002-0.2wt%
(2) alkaline-earth metal of 0.005-0.5wt%
(3) scandium of 0.05-0.5wt%
(4) cerium oxide of 0.06-1wt% and zirconia sol
(5) copper of 0.5-6wt%
(6) 5-25wt%, the more preferably silver of 8-22wt%
(7) carrier of 70-90wt%.
In the present invention, the gross weight of described catalyst refers to the weight of final obtained catalyst prod.
In catalyst of the present invention, described alkali metal salt be selected from lithium, sodium, potassium, rubidium, cesium element one or more.
In catalyst of the present invention, described alkali salt to be selected from magnesium, calcium, strontium, barium element one or more.
In catalyst of the present invention, in described cerium oxide and zirconia sol, the ratio of cerium oxide and zirconic amount of substance is 5:1 ~ 1:1, preferred 4:1-1:1.
In catalyst of the present invention, described catalyst carrier is selected from α-Al
2o
3, SiO
2, one or more in SiC, MgO or talcum powder, preferred α-Al
2o
3, MgO or talcum powder.
The auxiliary agents such as the alkali metal in catalyst of the present invention, alkaline-earth metal, scandium element, cerium oxide sol, zirconia sol especially scandium element effectively can improve reactivity worth and the structural stability of catalyst.
The preparation method of the support type composite metal catalyst for unsaturated alcohol oxidation of the present invention, comprises following steps:
(1), after soluble silver salt solution being precipitated with precipitating reagent, add amine aqueous solution and dissolved formation silver-amine aqueous solution;
(2) soluble copper salt, solubility scandium salts, alkali metal salt, alkali salt, auxiliary agent are added in the silver-amine aqueous solution of step (1) and obtain the first mixed liquor, or be mixed to get the second mixed liquor after mantoquita, scandium salts, alkali metal salt, alkali salt, auxiliary agent are dissolved separately formation amine complex liquid, described auxiliary agent is cerium oxide and zirconia, adds with solation;
(3) use the first mixed liquor spraying of gained in step (2) or the carrier of dip loading catalyst, or the second mixed liquor and silver-amine aqueous solution sprays respectively or the carrier of dip loading catalyst;
(4) the catalyst of gained in (3) is steamed and desolventize;
(5) roasting obtains final catalyst.
In the preparation method of catalyst of the present invention, described precipitating reagent is the mixture of ammonium oxalate, ammonium carbonate or both arbitrary proportions, preferred ammonium oxalate.Precipitating reagent relative to the excessive 25-100% of silver-colored mole, the excessive 50-70% of preferred mole.The concentration of precipitating reagent is 0.1-25mol/L, preferred 1-10mol/L.
In the preparation method of catalyst of the present invention, described amine aqueous solution be selected from ethylenediamine, ammonium hydroxide, the third triamine one or more, preferred ethylenediamine, the third triamine.Amine aqueous solution relative to the excessive 20-200% of silver-colored mole, the excessive 50-100% of preferred mole.The concentration of described amine aqueous solution is 0.1-15mol/L.
In the preparation method of catalyst of the present invention, described soluble silver salt be selected from silver fluoride, silver perchlorate, silver nitrate one or more, preferred liquor argenti nitratis ophthalmicus.The concentration of the silver salt solution of solubility is 0.1-50mol/L, preferred 1-20mol/L.
In the preparation method of catalyst of the present invention, described soluble copper salt to be selected from copper nitrate, copper chloride, copper sulphate any one or multiple arbitrary proportion mixture, preferred copper nitrate.
In the preparation method of catalyst of the present invention, described solubility scandium salts is any one or multiple mixture in scandium nitrate, scandium sulfate, scandium carbonate, preferred scandium nitrate.
In the preparation method of catalyst of the present invention, described alkali metal salt be selected from lithium, sodium, potassium, rubidium, the carbonate of cesium element or nitrate one or more.
In the preparation method of catalyst of the present invention, described alkali salt to be selected from magnesium, calcium, strontium, the nitrate of barium element or sulfate one or more.
In the preparation method of catalyst of the present invention, described cerium oxide and zirconia two kinds of colloidal sols all adopt titration method to prepare, and cerium oxide sol adopts the method preparation of ammonia water titration nitrous acid cerium, and zirconia adopts the preparation of ammonia water titration basic zirconium chloride method.
In the preparation method of catalyst of the present invention, step (3) described in the second mixed liquor can to spray before silver-amine aqueous solution or be impregnated on carrier or to spray simultaneously with silver-amine aqueous solution or be impregnated on carrier and also can spray after silver-amine aqueous solution or be impregnated on carrier.The process of spraying and dipping can a step or a point multistep complete.
In the preparation method of catalyst of the present invention, the step process that (4) middle steaming desolventizes can be air atmosphere can be also inert gas atmosphere, and temperature controls at 60-100 DEG C.
In the preparation method of catalyst of the present invention, step (5) in the temperature of roasting control at 200-600 DEG C, preferred 300-450 DEG C, the atmosphere of roasting can be air, nitrogen etc.The time controling of roasting at 0.1-3 hour, preferred 0.5-1 hour.
The unsaturated alcohol that catalyst of the present invention or the catalyst adopting method of the present invention to obtain are applicable to 3-12 carbon atom is oxidized to the reaction of carbonyls, preferably be applicable to the oxidation reaction of allyl alcohol, 2-butenol, 3-butene-2-ol, 3-cyclohexenol, 3-methyl-2 butenol, 3-methyl-3-butenol, be particularly preferably applicable to the reaction that 3-methyl-3-butenol and 3-methyl-2 butenol are oxidized to 3-methyl-3-crotonaldehyde and 3-methyl-2-butene aldehyde.
The detailed process of catalyst application of the present invention in unsaturated alcohol gas phase oxidation is as follows: select fixed bed reactors, and Catalyst packing, in the middle of reaction tube, is all filled with quartz sand up and down.In course of reaction, unsaturated alcohol enter together with nitrogen with air after preheater is heat vaporized reaction tube by reaction tube in catalyst layer react, react terminate rear generation aldehyde, the alcohol do not reacted, air, nitrogen and carbon monoxide, carbon dioxide, accessory substance, other organic matters etc. flow out reaction tube.Catalyst application of the present invention in the process conditions of unsaturated alcohol oxidation reaction is: reaction temperature is at 250-420 DEG C, and preferably at 320-380 DEG C, gas space velocity is at 3000-40000h
-1, better at 10000-25000h
-1, the gas composition of unstripped gas is unsaturated alcohol steam 10-25%, oxygen 6-12%, and all the other are inert nitrogen gas.
Catalyst of the present invention combines silver and the advantage of copper catalyst, simultaneously owing to adding the auxiliary agents such as scandium element, makes it to have the feature of active high, good stability.Be applicable to the oxidation reaction of unsaturated alcohol, be specially adapted to the reaction of 3-methyl-3-butenol or 3-methyl-2 butenol oxidation preparation 3-methyl-3-crotonaldehyde or 3-methyl-2-butene aldehyde.The conversion ratio of unsaturated alcohol is up to 70-75% in for 3-methyl-3-butenol oxidation reaction, and unsaturated aldehyde is selective reaches 96-97%, reacts in 1000 hours, and catalyst activity is stablized.The preparation method of catalyst of the present invention is simple, and the raw material used cheaply is easy to get, and is suitable for heavy industrialization application.
Detailed description of the invention
The analysis of product adopts the online gas-chromatography of Shimadzu to analyze.
Analytical conditions for gas chromatography:
Shimadzu GC-2014 on-line analysis gas-chromatography configures one ten logical high temperature sampling valve and two six-way valves, two flame ionization ditectors (FID) and a thermal conductivity cell detector (TCD), adopt the organic matter that DB-17 chromatographic column and FID detection reaction generate, 13X molecular sieve column detects CO, CO of constant and trace with damping column in conjunction with TCD and fid detector
2, O
2, N
2deng.
Chromatographic column: Shimadzu DB-17(specification is 50m × 0.32mm × 0.25mm)
Injector temperature: 280 DEG C
Split ratio: 30:1
Post flow: 1.5ml/min
Chromatographic column heating schedule: 50 DEG C keep 1min
5 DEG C/min is elevated to 280 DEG C, keeps 2min
Detector temperature: 280 DEG C, H
2flow: 35ml/min
Air mass flow: 350ml/min.
In the following Examples and Comparative Examples, the aqueous solution amount of skipping over containing active component in described impregnation steps, and directly dry after dipping, without the loss of component.
Embodiment 1
Take 1.45gAgNO
3be dissolved in 5ml water, 0.76g (NH
4)
2c
2o
4be dissolved in 8ml water, react under two solution being placed in 40 DEG C of stirring in water bath conditions.React washing precipitation after 1 hour, wash in the silver oxalate precipitate of 2-3 backward generation that to add 2ml molar concentration be that the ethylenediamine solution of 10mol/L obtains silver-amine complex liquid, in the silver-amine complex liquid of gained, add 0.015gCs
2cO
3, 0.60gCu (NO
3)
23H
2o, 0.35mgSc (NO
3)
33H
2o, 0.020gSr (CH3COO)
2, 0.010gZrO
2colloidal sol, 0.020gCeO
2colloidal sol is dissolved into homogeneous solution.By the α-Al of 5g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and at 100 DEG C, dry steaming desolventizes, and 260 DEG C of roastings obtain catalyst A 6.1g half an hour.Wherein, silver accounts for 15wt%, and copper accounts for 2.6wt%, and scandium accounts for 0.009wt%, and cerium oxide zirconia sol accounts for 0.5wt%.
The reactivity worth test of catalyst A: by catalyst breakage to 30-60 order, get 2ml load internal diameter be in the reaction tube of 1cm, air: nitrogen is 2:1, per hour enter raw material 3-methyl-3-butenol 12ml, enter air 7.5L, setting reacting initial temperature 355 DEG C, reaction focus is 386 DEG C, gas chromatographic analysis product, obtain reaction conversion ratio 70%, after 3-methyl-3-crotonaldehyde tautomerizes to 3-methyl-2-butene aldehyde selective 96%, Carbon balance 95%, yield 64%.
Catalyst A life test: continued operation under above-mentioned process conditions, every two hours sample analysis, in 1000 hours, reactivity has no decline, Conversion Selectivity parameter keeps stable always, after reaction carries out about 1200 hours, reaction conversion ratio starts to reduce, until after 1500 hours, conversion ratio is down to less than 10%.
Embodiment 2
Take 3.47gAgNO
3be dissolved in 5ml water, 2.17g (NH
4)
2c
2o
4be dissolved in 10ml water, react under two solution being placed in 40 DEG C of stirring in water bath conditions.React washing precipitation after 1 hour, wash in 2-3 backward silver oxalate precipitate and add the obtained silver-amine complex liquid of ethylenediamine dissolving that 2ml concentration is 15mol/L, in the silver-amine complex liquid of gained, add 0.015gCs
2cO
3, 0.14gCu (NO
3)
23H
2o, 0.43gSc
2(SO
4)
38H
2o, 0.020gSr (CH
3cOO)
2, 1.8mgZrO
2colloidal sol, 1.8mgCeO
2colloidal sol is dissolved into homogeneous solution.By the α-Al of 5g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and at 100 DEG C, dry steaming desolventizes, and 300 DEG C of roastings obtain catalyst B 7.4g half an hour, and wherein, silver accounts for 30wt%, and copper accounts for 0.5wt%, and scandium accounts for 1wt%, and cerium oxide zirconia sol accounts for 0.05wt%.
The reactivity worth test of catalyst B: by catalyst breakage to 30-60 order, get 2ml load internal diameter be in the reaction tube of 1cm, air: nitrogen is 2:1, per hour enter raw material 3-methyl-2 butenol 16ml, enter air 12L, setting reacting initial temperature 355 DEG C, hot(test)-spot temperature 380 DEG C, gas chromatographic analysis product, obtain reaction conversion ratio 75%, 3-methyl-2-butene aldehyde selective 96% after isomerization reaction, Carbon balance 96%, yield 69%.
Catalyst B life test: continued operation under above-mentioned process conditions, every two hours sample analysis, in 1000 hours, reactivity has no decline, Conversion Selectivity parameter keeps stable always, after reaction carries out about 1100 hours, reaction conversion ratio starts to reduce, until after 1300 hours, conversion ratio is down to less than 10%.
Embodiment 3
Take 0.16gAgNO
3be dissolved in 5ml water, 0.08g (NH
4)
2c
2o
4be dissolved in 5ml water, react under two solution being placed in 40 DEG C of stirring in water bath conditions.React washing precipitation after 1 hour, wash in the silver oxalate precipitate of 2-3 backward generation that to add 2ml concentration be that the third three amine solvents of 0.5mol/L obtain silver-amine complex liquid, in the silver-amine complex liquid of gained, add 0.03gCs
2cO
3, 1.65gCuSO
45H
2o, 0.24gSc (NO
3)
33H
2o, 0.040gSr (CH3COO)
2, 0.5gZrO
2colloidal sol, 0.5gCeO
2colloidal sol is dissolved into homogeneous solution.By the α-Al of 10g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and at 100 DEG C, dry steaming desolventizes, and 400 DEG C of roastings obtain catalyst C half an hour.Finally obtain catalyst C10.5g, wherein, silver accounts for 1wt%, and copper accounts for 4wt%, and scandium accounts for 0.4wt%, and cerium oxide zirconia sol accounts for 1wt%.
The reactivity worth test of catalyst C: by catalyst breakage to 30-60 order, getting 2ml loading internal diameter is in the reaction tube of 1cm, air: nitrogen is 2:1, per hour enter raw material allyl alcohol 15ml, enter air 10L, setting reacting initial temperature 355 DEG C, reaction focus is 385 DEG C, gas chromatographic analysis product, obtain reaction allyl alcohol conversion ratio 99%, allyl aldehyde selective 98%, Carbon balance 97%, yield 94%.
Catalyst C life test: continued operation under above-mentioned process conditions, every two hours sample analysis, in 1000 hours, reactivity has no decline, Conversion Selectivity parameter keeps stable always, after reaction carries out about 1100 hours, reaction conversion ratio starts to reduce, until after 1500 hours, conversion ratio is down to less than 50%.
Embodiment 4
Take 2gAgNO
3be dissolved in 5ml water, 1.2g (NH
4)
2c
2o
4be dissolved in 6ml water, react under two solution being placed in 40 DEG C of stirring in water bath conditions.React washing precipitation after 1 hour, the silver oxalate precipitate washing 2-3 backward generation adds the obtained silver-amine complex liquid of ethylenediamine dissolving that 2ml concentration is 15mol/L, in the silver-amine complex liquid of gained, add 0.015gCs
2cO
3, 2.68gCu (NO
3)
23H
2o, 0.20gSc (NO
3)
33H
2o, 0.020gSr (CH
3cOO)
2, 0.010gZrO
2colloidal sol, 0.020gCeO
2colloidal sol is dissolved into homogeneous solution.By the α-Al of 5g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and at 100 DEG C, dry steaming desolventizes, and 450 DEG C of roastings obtain catalyst D half an hour.Finally obtain catalyst D7.1g, wherein silver accounts for 18wt%, and copper accounts for 10wt%, and scandium accounts for 0.5wt%, and cerium oxide zirconia sol accounts for 0.4wt%.
The reactivity worth test of catalyst D: by catalyst breakage to 30-60 order, get 2ml load internal diameter be in the reaction tube of 1cm, per hour enter raw material 2-butenol 15ml, enter air 7.5L, nitrogen 5L, setting reacting initial temperature 400 DEG C, reaction focus is 430 DEG C, gas chromatographic analysis product, obtain reaction conversion ratio 96%, 2-crotonaldehyde selective 98%, Carbon balance 97%, yield 91%.
Catalyst D life test: continued operation under above-mentioned process conditions, every two hours sample analysis, in 1000 hours, reactivity has no decline, Conversion Selectivity parameter keeps stable always, after reaction carries out about 1200 hours, reaction conversion ratio starts to reduce, until after 1500 hours, conversion ratio is down to less than 50%.
Comparative example 1
Take 6.69gCu (NO
3)
23H
2it is form amine complex liquid in third triamine solution of 5mol/L that O dissolves in 4ml concentration, adds 0.05gCs
2cO
3and 0.08gSr (CH
3cOO)
2dissolve and form uniform maceration extract.By the α-Al of 10g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and at 100 DEG C, dry steaming desolventizes, and 300 DEG C of roastings obtain catalyst E half an hour.Finally obtain catalyst E11.8g, wherein, copper accounts for 15wt%.
The reactivity worth test of catalyst E: repeat embodiment 1, reaction focus is 380 DEG C, gas chromatographic analysis bearing reaction conversion ratio 57%, after isomerization reaction selective 91%, Carbon balance 95%, yield 49%.
Catalyst E life test: in the detecting catalyst life-span under the process conditions identical with embodiment 1, after 240 hours, reactivity starts to drop to conversion ratio 40%, selective 75%, decline gradually afterwards, constantly little to reaction 360, reach conversion ratio 20%, selective 50%.
Comparative example 2
Take 7.2gAgNO
3be dissolved in 5ml water, 3.88g (NH
4)
2c
2o
4be dissolved in 6ml water, react under two solution being placed in 40 DEG C of stirring in water bath conditions.React washing precipitation after 1 hour, being that the ethylenediamine solution of 10mol/L obtains silver-amine complex liquid by adding 5ml concentration in the silver oxalate precipitate of generation after washing 2-3 time, in the silver-amine complex liquid of gained, adding 0.020gCs
2cO
3, 0.020gSr (CH
3cOO)
2, be dissolved into homogeneous solution.By the α-Al of 10g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and at 100 DEG C, dry steaming desolventizes, and 400 DEG C of roastings obtain catalyst F14.7g half an hour, and wherein silver accounts for 31wt%.
The reactivity worth test of catalyst F: repeat the operating condition of embodiment 2, reaction focus is 376 DEG C, gas chromatographic analysis bearing reaction conversion ratio 45%, after isomerization reaction selective 70%, Carbon balance 95%, yield 30%.
The life test of catalyst F: in the detecting catalyst life-span under the process conditions identical with embodiment 2, after 120 hours, reactivity starts to drop to conversion ratio 35%, selective 50%, decline gradually afterwards, constantly little to reaction 600, reach conversion ratio 20%, selective 30%.
Comparative example 3
Take 0.32gAgNO
3be dissolved in 5ml water, 0.2g (NH
4)
2c
2o
4be dissolved in 5ml water, react under two solution being placed in 40 DEG C of stirring in water bath conditions.React washing precipitation after 1 hour, being that the ethylenediamine solution of 2mol/L obtains silver-amine complex liquid by adding 2ml concentration in the silver oxalate precipitate of generation after washing 2-3 time, in the silver-amine complex liquid of gained, adding 0.015gCs
2cO
3, 0.020gSr (CH3COO)
2, add ZrO in powder form
20.05gCeO
20.05g is dissolved into homogeneous solution.By the α-Al of 10g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and at 100 DEG C, dry steaming desolventizes, and 450 DEG C of roastings obtain catalyst G half an hour.Finally obtain catalyst G10.3g, wherein, silver accounts for 2wt%, and cerium oxide zirconia accounts for 1wt%.
The reactivity worth test of catalyst G: repeat embodiment 3, reaction focus is 376 DEG C, gas chromatographic analysis bearing reaction conversion ratio 56%, selective 90%, Carbon balance 96%, yield 48%.
Catalyst G life test: in the detecting catalyst life-span under the process conditions identical with embodiment 3, after 360 hours, reactivity starts to drop to conversion ratio 45%, selective 85%, decline gradually afterwards, constantly little to reaction 600, reach conversion ratio 20%, selective 60%.
Claims (19)
1., for a support type composite metal catalyst for unsaturated alcohol oxidation, it is characterized in that: in overall catalyst weight, catalyst comprises:
(1) alkali metal of 0.001-0.3wt%
(2) alkaline-earth metal of 0.001-1wt%
(3) scandium of 0.001-1wt%
(4) cerium oxide of 0.05-1wt% and zirconia
(5) copper of 0.3-10wt%
(6) silver of 1-30wt%
(7) carrier of 60-95wt%.
2. catalyst as claimed in claim 1, it is characterized in that: in overall catalyst weight, catalyst comprises:
(1) alkali metal of 0.002-0.2wt%
(2) alkaline-earth metal of 0.005-0.5wt%
(3) scandium of 0.05-0.5wt%
(4) cerium oxide of 0.06-1wt% and zirconia
(5) copper of 0.5-6wt%
(6) silver of 5-25wt%
(7) carrier of 70-90wt%.
3. catalyst as claimed in claim 1 or 2, is characterized in that: described alkali metal be selected from lithium, sodium, potassium, rubidium, cesium element one or more.
4. catalyst as claimed in claim 1 or 2, is characterized in that: described alkaline-earth metal to be selected from magnesium, calcium, strontium, barium one or more.
5. catalyst as claimed in claim 1 or 2, is characterized in that: described carrier is selected from α-Al
2o
3, SiO
2, one or more in SiC, MgO or talcum powder.
6. catalyst as claimed in claim 1 or 2, is characterized in that: in described cerium oxide and zirconia, the ratio of cerium oxide and zirconic amount of substance is 5:1 ~ 1:1.
7. catalyst as claimed in claim 6, is characterized in that: in described cerium oxide and zirconia, the ratio of cerium oxide and zirconic amount of substance is 4:1 ~ 1:1.
8. the preparation method of the catalyst according to any one of claim 1-7, is characterized in that, comprises the following steps:
(1), after soluble silver salt solution being precipitated with precipitating reagent, add amine aqueous solution and dissolved formation silver-amine aqueous solution;
(2) soluble copper salt, solubility scandium salts, alkali metal salt, alkali salt, auxiliary agent are added in step silver-amine aqueous solution (1) and obtain the first mixed liquor, or be mixed to get the second mixed liquor after mantoquita, scandium salts, alkali metal salt, alkali salt, auxiliary agent are dissolved separately formation amine complex liquid, described auxiliary agent is cerium oxide and zirconia, adds with solation;
With step (2) in the first mixed liquor spraying or carrier of dip loading catalyst of gained, or the second mixed liquor and silver-amine aqueous solution sprays respectively or the carrier of dip loading catalyst;
By step (3) in gained catalyst steam desolventize;
(5) roasting obtains final catalyst.
9. preparation method according to claim 8, it is characterized in that: described precipitating reagent is the mixture of ammonium oxalate or ammonium carbonate or both arbitrary proportions, precipitating reagent is relative to the excessive 25-100% of silver-colored mole, described amine aqueous solution be selected from ethylenediamine, ammonium hydroxide, the third triamine one or more, amine aqueous solution is relative to the excessive 20-200% of silver-colored mole.
10. preparation method according to claim 9, is characterized in that: described precipitating reagent is ammonium oxalate, and precipitating reagent is relative to the excessive 50-70% of silver-colored mole; Described amine aqueous solution is selected from ethylenediamine or the third triamine, and amine aqueous solution is relative to the excessive 50-100% of silver-colored mole.
11. preparation methods according to claim 8, is characterized in that: the concentration that described soluble silver salt solution is selected from one or more soluble silver salt solution in silver fluoride, silver perchlorate, silver nitrate is 0.1-50mol/L.
12. preparation methods according to claim 11, is characterized in that: described soluble silver salt solution is selected from liquor argenti nitratis ophthalmicus, and the concentration of soluble silver salt solution is 1-20mol/L.
13. preparation methods according to claim 8, is characterized in that: soluble copper salt to be selected from copper nitrate, copper chloride, copper sulphate any one or multiple; Described alkali metal salt be selected from lithium, sodium, potassium, rubidium, the carbonate of cesium element or nitrate one or more, described alkali salt to be selected from magnesium, calcium, strontium, the nitrate of barium element or sulfate one or more.
14. preparation methods according to Claim 8 according to any one of-13, is characterized in that: described solubility scandium salts be in scandium nitrate, scandium sulfate, scandium carbonate one or more.
15. preparation methods according to Claim 8 according to any one of-13, it is characterized in that: the (4) in step, it is air atmosphere or inert gas atmosphere that catalyst steams the process desolventized, steaming the process temperature desolventized controls at 60-100 DEG C, the (5) in step the temperature of roasting control at 200-600 DEG C, the atmosphere of roasting is air or nitrogen, and the time controling of roasting is at 0.1-3 hour.
16. preparation methods according to claim 15, is characterized in that: the (5) in step the temperature of roasting control at 300-450 DEG C, the time controling of roasting is at 0.5-1 hour.
17. according to any one of claim 1-7 the purposes of the catalyst that preparation method obtains according to any one of catalyst or claim 8-16, it is characterized in that: this catalyst is applicable to the oxidation reaction of the unsaturated alcohol of 3-12 carbon atom.
18. purposes according to claim 17, is characterized in that: this catalyst is applicable to the oxidation reaction of allyl alcohol, 2-butenol, 3-butene-2-ol, 3-cyclohexenol, 3-methyl-2 butenol, 3-methyl-3-butenol.
19. purposes according to claim 18, is characterized in that: this catalyst is applicable to the reaction that 3-methyl-3-butenol and 3-methyl-2 butenol are oxidized to 3-methyl-3-crotonaldehyde and 3-methyl-2-butene aldehyde.
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| CN106975495A (en) * | 2017-03-10 | 2017-07-25 | 华东师范大学 | A kind of preparation and its application of carborundum supported copper bimetallic catalyst |
| CN107812531B (en) * | 2017-10-19 | 2020-06-16 | 万华化学集团股份有限公司 | Catalyst for preparing ethylenically unsaturated aldehyde from ethylenically unsaturated alcohol, preparation method and application thereof |
| CN108014797B (en) * | 2017-12-08 | 2020-08-28 | 万华化学集团股份有限公司 | Supported silver monoatomic catalyst for oxidizing unsaturated multi-carbon alcohol and preparation method thereof |
| CN108452799B (en) * | 2018-05-10 | 2021-06-22 | 北京化工大学 | Preparation method of supported silver catalyst and application of supported silver catalyst in preparation of benzaldehyde by catalyzing anaerobic dehydrogenation of benzyl alcohol |
| WO2020099390A1 (en) | 2018-11-13 | 2020-05-22 | Basf Se | Catalyst bed comprising silver catalyst bodies and process for the oxidative dehydrogenation of olefinically unsaturated alcohols |
| CN111229216B (en) * | 2018-11-29 | 2022-08-05 | 万华化学集团股份有限公司 | Eggshell type silver catalyst and preparation method and application thereof |
| CN114380677B (en) * | 2020-10-16 | 2023-12-19 | 万华化学集团股份有限公司 | Preparation method of 3-methyl-2-butenal |
| WO2023099727A1 (en) | 2021-12-03 | 2023-06-08 | Basf Se | Process for preparing isoprenal and/or prenal |
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| US4165342A (en) * | 1977-04-05 | 1979-08-21 | Basf Aktiengesellschaft | Preparation of 3-alkyl-buten-1-als |
| US6013843A (en) * | 1997-05-28 | 2000-01-11 | Basf Aktiengeselllschaft | Continuous industrial production of unsaturated aliphatic aldehydes in a tube bundle reactor |
| 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 |
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| JPS60246340A (en) * | 1984-05-21 | 1985-12-06 | Kuraray Co Ltd | Preparation of 3-methyl-2-buten-1-ol |
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| US4165342A (en) * | 1977-04-05 | 1979-08-21 | Basf Aktiengesellschaft | Preparation of 3-alkyl-buten-1-als |
| US6013843A (en) * | 1997-05-28 | 2000-01-11 | Basf Aktiengeselllschaft | Continuous industrial production of unsaturated aliphatic aldehydes in a tube bundle reactor |
| 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 |
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