CN103769162A - Loaded composite metal catalyst used for unsaturated alcohol oxidation and preparation method thereof - Google Patents
Loaded composite metal catalyst used for unsaturated alcohol oxidation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a load composite metal catalyst used for unsaturated alcohol oxidation and a preparation method thereof. The catalyst comprises: 0.001-0.3wt% of an alkali metal, 0.001-1wt% of an alkaline earth metal, 0.001-1wt% of scandium, 0.05-1wt% of cerium oxide and zirconia sol, 0.3-10wt% of copper, 1-30wt% of silver, and 60-95wt% of a carrier. The preparation method includes: using a precipitant to precipitate a silver salt solution, making the obtained silver precipitate into a silver-amine solution by an amine compound, employing an amine complexing solution of a soluble copper salt, a scandium salt, an alkali metal salt, an alkaline earth metal salt and additives to spray or dip the catalyst carrier, and then carrying out drying and roasting to obtain the loaded silver-copper composite catalyst. The catalyst provided by the invention has the characteristics of high reactivity, good stability and fewer three wastes, etc., thus being 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, the oxidizing process that alcohol is oxidized to carbonyls is all occupied critical role.From chemical property and in various uses, carbonyls occupies special critical positions, the beginning raw material that they synthesize often.This namely aldehyde, ketone become the particularly important source material of fine chemistry industry process and the reason of intermediate of chemical process, therefore alcohol being oxidized to corresponding carbonyls is one of most important course of reaction in organic chemistry.Conventional oxidation method, need to be used plurality of heavy metal reagent on the one hand, has increased cost of material; On the other hand, course of reaction produce a large amount of discarded object severe contaminations environment.The environmental pollution becoming increasingly conspicuous is now also one makes us stubborn problem, so how to address these problems is more and more subject to people's attention.Therefore no matter from economic angle, or the viewpoint of protection of the environment and sustainable development, in the urgent need to the green dioxygen oxidation method of development 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 and carry out gas phase oxidation dehydrogenation reaction and generate with air or oxygen the good catalyst of aldehydes or ketones.Existing a lot of patent and bibliographical information the catalytic performance of such catalyst to unsaturated alcohol oxidative dehydrogenation, but these metallic catalysts all exist shortcoming separately.Though silver catalyst is better to unsaturated alcohol oxidation activity, there is higher yield and selective, under hot conditions, the easy sintering of catalyst is assembled, 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, selectively very low, cannot realize industrialized requirement.Silver-colored and copper are smelted into alloy and need to consume a large amount of man power and materials, and operating process is loaded down with trivial details, implements difficulty larger.And although Au catalyst reactivity is fine, expensive, greatly increase the cost of production process.
3-methyl-2-butene aldehyde is a kind of important industrial chemicals, and they can be for the manufacture of dyestuff, pesticide, medicine, plastics, vitamin, spices etc.US2042220 has told about 3-methyl-2-butene aldehyde and can have been made 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 by reducing and make under 300 ℃ of hydrogen conditions of Cu oxide particle.Patent DE-B2517859 described 3-methyl-3-butenol under the condition that does not have oxygen take metallic copper as catalyst, produced a large amount of formaldehyde accessory substances, significantly reduce several days inner catalysts are active, therefore have no alternative but to carry out the frequent regeneration of catalyst.
DE-B 2715209 and EP-B 55354 have described the process that 3-methyl-3-butenol carries out oxidative dehydrogenation take silver or copper crystal as catalyst under oxygen existence condition, the shortcoming of this process is that catalyst costs is very high, only distribute relatively evenly or in layer structure, have when certain particle diameter distributes at silver catalyst particle diameter and just can obtain, even in some example, need the particular combinations of silver and copper catalyst, therefore be not only reactor and handle costliness, catalyst is also difficult to repeat, in addition, the higher reaction temperature using in this process can make sintering of catalyst, thereby cause pressure rise.
BASF patent US5149884 and US6013843 adopt shell and tube reactor to carry out 3-methyl-3-butenol to be oxidized to the reaction of 3-methyl-2-butene aldehyde take fine silver particle as catalyst, conversion ratio can reach 52-55%, selective 90-92%.
In view of the variety of issue of unsaturated alcohol oxidation reaction catalyst existence, in the urgent need to developing the catalyst that new activity is high and stable.
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 that is provided for unsaturated alcohol oxidation, and this preparation technology is simple, cost is low.
The 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, with the total restatement of catalyst, 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, with the total restatement of catalyst, 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 the catalyst prod finally making.
In catalyst of the present invention, described alkali metal salt is selected from one or more in lithium, sodium, potassium, rubidium, cesium element.
In catalyst of the present invention, described alkali salt is 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, preferably 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, preferably α-Al
2o
3, MgO or talcum powder.
The auxiliary agents such as alkali metal in catalyst of the present invention, alkaline-earth metal, scandium element, cerium oxide sol, zirconia sol especially scandium element can effectively 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 silver soluble salting liquid being precipitated with precipitating reagent, add amine aqueous solution to be dissolved and form 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 after being dissolved separately to formation amine complex liquid, mantoquita, scandium salts, alkali metal salt, alkali salt, auxiliary agent be mixed to get the second mixed liquor, 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 desolventized;
(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, preferably ammonium oxalate.Precipitating reagent is with respect to the excessive 25-100% of silver-colored mole, preferably the excessive 50-70% of mole.The concentration of precipitating reagent is 0.1-25mol/L, preferably 1-10mol/L.
In the preparation method of catalyst of the present invention, described amine aqueous solution is selected from one or more in ethylenediamine, ammonium hydroxide, the third triamine, preferably ethylenediamine, the third triamine.Amine aqueous solution is with respect to the excessive 20-200% of silver-colored mole, preferably the excessive 50-100% of mole.The concentration of described amine aqueous solution is 0.1-15 mol/L.
In the preparation method of catalyst of the present invention, described soluble silver salt is selected from one or more in silver fluoride, silver perchlorate, silver nitrate, preferably liquor argenti nitratis ophthalmicus.The concentration of the silver salt solution of solubility is 0.1-50 mol/L, preferably 1-20 mol/L.
In the preparation method of catalyst of the present invention, described soluble copper salt is selected from copper nitrate, copper chloride, copper sulphate any one or multiple arbitrary proportion mixture, preferably 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, preferably scandium nitrate.
In the preparation method of catalyst of the present invention, described alkali metal salt is selected from one or more in carbonate or the nitrate of lithium, sodium, potassium, rubidium, cesium element.
In the preparation method of catalyst of the present invention, described alkali salt is selected from the nitrate of magnesium, calcium, strontium, barium element or sulfate one or more.
In the preparation method of catalyst of the present invention, two kinds of colloidal sols of described cerium oxide and zirconia all adopt titration method preparation, 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, second mixed liquor of step described in (3) can spray or be impregnated into spray simultaneously or be impregnated on carrier on carrier or with silver-amine aqueous solution and also can after silver-amine aqueous solution, spray or be impregnated on carrier before silver-amine aqueous solution.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 that air atmosphere can be also inert gas atmosphere, and temperature is controlled at 60-100 ℃.
In the preparation method of catalyst of the present invention, the step (5) temperature of middle roasting is controlled at 200-600 ℃, preferably 300-450 ℃, and the atmosphere of roasting can be air, nitrogen etc.The time of roasting is controlled at 0.1-3 hour, preferably 0.5-1 hour.
The unsaturated alcohol that catalyst of the present invention or the catalyst that adopts method of the present invention to make 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 3-methyl-3-butenol and 3-methyl-2 butenol and be oxidized to the reaction of 3-methyl-3-crotonaldehyde and 3-methyl-2-butene aldehyde.
It is as follows that catalyst of the present invention is applied to detailed process in unsaturated alcohol gas phase oxidation: select fixed bed reactors, Catalyst packing, in the middle of reaction tube, is all filled with quartz sand up and down.In course of reaction, unsaturated alcohol after preheater heating vaporization, enter together with nitrogen with air reaction tube by reaction tube in catalyst layer react, reaction finishes the aldehyde of rear generation, the alcohol not reacting, air, nitrogen and carbon monoxide, carbon dioxide, accessory substance, other organic matters etc. and flows out reaction tube.The process conditions that catalyst of the present invention is applied to unsaturated alcohol oxidation reaction are: reaction temperature, at 250-420 ℃, is preferably in 320-380 ℃, and gas compartment speed is at 3000-40000h
-1, better at 10000-25000 h
-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 having added 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.At the conversion ratio for 3-methyl-3-butenol oxidation reaction unsaturated alcohol, up to 70-75%, unsaturated aldehyde selectively reaches 96-97%, and reaction is in 1000 hours, and catalyst activity is stable.The preparation method of catalyst of the present invention is simple, and the raw material using is cheaply easy to get, and is suitable for heavy industrialization application.
The specific embodiment
The analysis of product adopts the online gas-chromatography of Shimadzu to analyze.
Analytical conditions for gas chromatography:
One ten logical high temperature sampling valve of Shimadzu GC-2014 on-line analysis gas-chromatography configuration and two six-way valves, two flame ionization ditectors (FID) and a thermal conductivity cell detector (TCD), the organic matter that adopts DB-17 chromatographic column and FID detection reaction to generate, 13X molecular sieve column is combined CO, the CO of TCD and fid detector detection constant and trace with damping column
2, O
2, N
2deng.
Chromatographic column: Shimadzu DB-17(specification is 50m × 0.32mm × 0.25mm)
Injector temperature: 280 ℃
Split ratio: 30:1
Post flow: 1.5ml/min
Chromatographic column heating schedule: 50 ℃ keep 1min
5 ℃/min is elevated to 280 ℃, keeps 2min
Detector temperature: 280 ℃, H
2flow: 35ml/min
Air mass flow: 350ml/min.
In the following Examples and Comparative Examples, the aqueous solution that contains active component in described impregnation steps is slightly excessive, and directly dries after dipping, without the loss of component.
Embodiment 1
Take 1.45 g AgNO
3be dissolved in 5 ml water 0.76g (NH
4)
2c
2o
4be dissolved in 8 ml water, two solution are placed under 40 ℃ of stirring in water bath conditions and are reacted.React washing precipitation after 1 hour, wash that in the silver oxalate precipitation of 2-3 backward generation, to add 2 ml molar concentrations be that the ethylenediamine solution of 10 mol/L makes silver-amine complex liquid, in silver-amine complex liquid of gained, add 0.015 g Cs
2cO
3, 0.60g Cu (NO
3)
23H
2o, 0.35 mg Sc (NO
3)
33H
2o, 0.020 g Sr (CH3COO)
2, 0.010 g ZrO
2colloidal sol, 0.020 g CeO
2colloidal sol is dissolved into homogeneous solution.By α-Al of 5 g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and dry steaming desolventizes at 100 ℃, and 260 ℃ of roastings obtain catalyst A 6.1 g half an hour.Wherein, silver accounts for 15wt%, and copper accounts for 2.6wt%, and scandium accounts for 0.009 wt%, and cerium oxide zirconia sol accounts for 0.5 wt%.
The reactivity worth test of catalyst A: by catalyst breakage to 30-60 order, get 2 ml and pack in the reaction tube that internal diameter is 1 cm, air: nitrogen is 2:1, per hour enter raw material 3-methyl-3-butenol 12 ml, enter air 7.5 L, set 355 ℃ of reacting initial temperatures, reaction focus is 386 ℃, gas chromatographic analysis product, obtain reaction conversion ratio 70%, 3-methyl-3-crotonaldehyde tautomerizes to after 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, it is stable that conversion ratio selectivity parameter keeps always, reaction was carried out after approximately 1200 hours, reaction conversion ratio starts to reduce, until after 1500 hours, conversion ratio is down to below 10 %.
Embodiment 2
Take 3.47 g AgNO
3be dissolved in 5 ml water 2.17 g (NH
4)
2c
2o
4be dissolved in 10 ml water, two solution are placed under 40 ℃ of stirring in water bath conditions and are reacted.React washing precipitation after 1 hour, wash that in 2-3 backward silver oxalate precipitation, to add 2 ml concentration be that the ethylenediamine of 15 mol/L dissolves and makes silver-amine complex liquid, in silver-amine complex liquid of gained, add 0.015 g Cs
2cO
3, 0.14 g Cu (NO
3)
23H
2o, 0.43 g Sc
2(SO
4)
38H
2o, 0.020 g Sr (CH
3cOO)
2, 1.8 mg ZrO
2colloidal sol, 1.8 mg CeO
2colloidal sol is dissolved into homogeneous solution.By α-Al of 5 g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and dry steaming desolventizes at 100 ℃, and 300 ℃ 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 2 ml and pack in the reaction tube that internal diameter is 1 cm, air: nitrogen is 2:1, per hour enter raw material 3-methyl-2 butenol 16 ml, enter air 12 L, set 355 ℃ of reacting initial temperatures, 380 ℃ of hot(test)-spot temperatures, gas chromatographic analysis product, obtain reaction conversion ratio 75%, after isomerization reaction, 3-methyl-2-butene aldehyde is selective 96%, 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, it is stable that conversion ratio selectivity parameter keeps always, reaction was carried out after approximately 1100 hours, reaction conversion ratio starts to reduce, until after 1300 hours, conversion ratio is down to below 10 %.
Embodiment 3
Take 0.16 g AgNO
3be dissolved in 5 ml water 0.08 g (NH
4)
2c
2o
4be dissolved in 5 ml water, two solution are placed under 40 ℃ of stirring in water bath conditions and are reacted.React washing precipitation after 1 hour, wash that in the silver oxalate precipitation of 2-3 backward generation, to add 2 ml concentration be that the third three amine solvents of 0.5 mol/L make silver-amine complex liquid, in silver-amine complex liquid of gained, add 0.03 g Cs
2cO
3, 1.65 g CuSO
45H
2o, 0.24 g Sc (NO
3)
33H
2o, 0.040 g Sr (CH3COO)
2, 0.5 g ZrO
2colloidal sol, 0.5 g CeO
2colloidal sol is dissolved into homogeneous solution.By α-Al of 10 g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and dry steaming desolventizes at 100 ℃, and 400 ℃ of roastings obtain catalyst C half an hour.Finally obtain catalyst C10.5 g, 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: catalyst breakage, to 30-60 order, is got to 2 ml and packed in the reaction tube that internal diameter is 1 cm, air: nitrogen is 2:1, per hour enter raw material allyl alcohol 15 ml, enter air 10 L, set 355 ℃ of reacting initial temperatures, reaction focus is 385 ℃, gas chromatographic analysis product, obtain reacting 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, it is stable that conversion ratio selectivity parameter keeps always, reaction was carried out after approximately 1100 hours, reaction conversion ratio starts to reduce, until after 1500 hours, conversion ratio is down to below 50 %.
Embodiment 4
Take 2 g AgNO
3be dissolved in 5 ml water 1.2 g (NH
4)
2c
2o
4be dissolved in 6 ml water, two solution are placed under 40 ℃ of stirring in water bath conditions and are reacted.React washing precipitation after 1 hour, it is that the ethylenediamine of 15 mol/L dissolves and makes silver-amine complex liquid that the silver oxalate precipitation of washing 2-3 backward generation adds 2 ml concentration, in silver-amine complex liquid of gained, adds 0.015 g Cs
2cO
3, 2.68 g Cu (NO
3)
23H
2o, 0.20 g Sc (NO
3)
33H
2o, 0.020 g Sr (CH
3cOO)
2, 0.010 g ZrO
2colloidal sol, 0.020 g CeO
2colloidal sol is dissolved into homogeneous solution.By α-Al of 5 g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and dry steaming desolventizes at 100 ℃, and 450 ℃ of roastings obtain catalyst D half an hour.Finally obtain catalyst D 7.1 g, wherein silver accounts for 18 wt%, and copper accounts for 10 wt%, and scandium accounts for 0.5wt%, and cerium oxide zirconia sol accounts for 0.4 wt%.
The reactivity worth test of catalyst D: by catalyst breakage to 30-60 order, get 2 ml and pack in the reaction tube that internal diameter is 1 cm, per hour enter raw material 2-butenol 15 ml, enter air 7.5 L, nitrogen 5L, set 400 ℃ of reacting initial temperatures, reaction focus is 430 ℃, gas chromatographic analysis product, obtain reaction conversion ratio 96%, 2-crotonaldehyde is 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, it is stable that conversion ratio selectivity parameter keeps always, reaction was carried out after approximately 1200 hours, reaction conversion ratio starts to reduce, until after 1500 hours, conversion ratio is down to below 50 %.
Comparative example 1
Take 6.69 g Cu (NO
3)
23H
2o dissolves in the third triamine solution that 4 ml concentration are 5 mol/L and forms amine complex liquid, adds 0.05 g Cs
2cO
3and 0.08 g Sr (CH
3cOO)
2dissolve and form uniform maceration extract.By α-Al of 10 g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and dry steaming desolventizes at 100 ℃, and 300 ℃ of roastings obtain catalyst E half an hour.Finally obtain catalyst E 11.8 g, wherein, copper accounts for 15 wt%.
The reactivity worth test of catalyst E: repeat embodiment 1, reaction focus is 380 ℃, gas chromatographic analysis bearing reaction conversion ratio 57%, selective 91% after isomerization reaction, 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, when reacting 360 hours, reach conversion ratio 20%, selective 50%.
Comparative example 2
Take 7.2 g AgNO
3be dissolved in 5 ml water 3.88 g (NH
4)
2c
2o
4be dissolved in 6 ml water, two solution are placed under 40 ℃ of stirring in water bath conditions and are reacted.React washing precipitation after 1 hour, washing after 2-3 time adding 5 ml concentration in the silver oxalate precipitation of generation is that the ethylenediamine solution of 10 mol/L makes silver-amine complex liquid, in silver-amine complex liquid of gained, adds 0.020 g Cs
2cO
3, 0.020 g Sr (CH
3cOO)
2, be dissolved into homogeneous solution.By α-Al of 10 g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and dry steaming desolventizes at 100 ℃, and 400 ℃ of roastings obtain catalyst F 14.7 g half an hour, and wherein silver accounts for 31 wt%.
The reactivity worth test of catalyst F: repeat the operating condition of embodiment 2, reaction focus is 376 ℃, gas chromatographic analysis bearing reaction conversion ratio 45%, selective 70% after isomerization reaction, 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, when reacting 600 hours, reach conversion ratio 20%, selective 30%.
Comparative example 3
Take 0.32 g AgNO
3be dissolved in 5 ml water 0.2 g (NH
4)
2c
2o
4be dissolved in 5 ml water, two solution are placed under 40 ℃ of stirring in water bath conditions and are reacted.React washing precipitation after 1 hour, washing after 2-3 time adding 2 ml concentration in the silver oxalate precipitation of generation is that the ethylenediamine solution of 2 mol/L makes silver-amine complex liquid, in silver-amine complex liquid of gained, adds 0.015 g Cs
2cO
3, 0.020 g Sr (CH3COO)
2, add ZrO with powder type
20.05 g CeO
20.05 g is dissolved into homogeneous solution.By α-Al of 10 g
2o
3carrier is added in above-mentioned solution, stir about 1 hour, and dry steaming desolventizes at 100 ℃, and 450 ℃ of roastings obtain catalyst G half an hour.Finally obtain catalyst G 10.3 g, wherein, silver accounts for 2 wt%, and cerium oxide zirconia accounts for 1wt%.
The reactivity worth test of catalyst G: repeat embodiment 3, reaction focus is 376 ℃, 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, when reacting 600 hours, reach conversion ratio 20%, selective 60%.
Claims (12)
1. for a support type composite metal catalyst for unsaturated alcohol oxidation, it is characterized in that: with the total restatement of catalyst, 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%
Preferred 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%.
2. catalyst as claimed in claim 1, is characterized in that: described alkali metal is selected from one or more in lithium, sodium, potassium, rubidium, cesium element.
3. catalyst as claimed in claim 1, is characterized in that: described alkaline-earth metal is selected from magnesium, calcium, strontium, barium one or more.
4. catalyst as claimed in claim 1, is characterized in that: described carrier is selected from α-Al
2o
3, SiO
2, one or more in SiC, MgO or talcum powder.
5. the catalyst as described in any one in claim 1-4, is characterized in that: in described cerium oxide and zirconia sol, the ratio of cerium oxide and zirconic amount of substance is 5:1 ~ 1:1, preferably 4:1 ~ 1:1.
6. according to the preparation method of the catalyst described in any one in claim 1-5, it is characterized in that, comprise the following steps:
(1), after silver soluble salting liquid being precipitated with precipitating reagent, add amine aqueous solution to be dissolved and form 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 after being dissolved separately to formation amine complex liquid, mantoquita, scandium salts, alkali metal salt, alkali salt, auxiliary agent be mixed to get the second mixed liquor, described auxiliary agent is cerium oxide and zirconia, adds with solation;
With step (2) in the first mixed liquor spraying of gained 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;
By step (3) in gained catalyst steam desolventize;
(5) roasting obtains final catalyst.
7. preparation method according to claim 6, it is characterized in that: described precipitating reagent is the mixture of ammonium oxalate or ammonium carbonate or both arbitrary proportions, preferably ammonium oxalate, precipitating reagent is with respect to the excessive 25-100% of silver-colored mole, the preferably excessive 50-70% of mole; Described amine aqueous solution is selected from one or more in ethylenediamine, ammonium hydroxide, the third triamine, preferably ethylenediamine or the third triamine, and amine aqueous solution is with respect to the excessive 20-200% of silver-colored mole, the preferably excessive 50-100% of mole.
8. preparation method according to claim 6, it is characterized in that: described silver soluble salting liquid is selected from one or more in silver fluoride, silver perchlorate, silver nitrate, preferably liquor argenti nitratis ophthalmicus, the concentration of silver soluble salting liquid is 0.1-50 mol/L, preferably 1-20 mol/L.
9. preparation method according to claim 6, is characterized in that: soluble copper salt be selected from copper nitrate, copper chloride, copper sulphate any one or multiple, preferably copper nitrate; Described alkali metal salt is selected from one or more in carbonate or the nitrate of lithium, sodium, potassium, rubidium, cesium element, and described alkali salt is selected from the nitrate of magnesium, calcium, strontium, barium element or sulfate one or more.
10. according to the preparation method described in any one in claim 6-9, it is characterized in that: described solubility scandium salts be in scandium nitrate, scandium sulfate, scandium carbonate one or more, preferably scandium nitrate.
11. according to the preparation method described in any one in claim 6-10, it is characterized in that: the (4) in step, it is air atmosphere or inert gas atmosphere that catalyst steams the process desolventizing, the process temperature that steaming desolventizes is controlled at 60-100 ℃, the (5) in step the temperature of roasting be controlled at 200-600 ℃, preferably 300-450 ℃, the atmosphere of roasting is air or nitrogen, the time of roasting is controlled at 0.1-3 hour, preferably 0.5-1 hour.
12. catalyst that make according to preparation method described in any one in catalyst described in any one in claim 1-5 or claim 6-11, it is characterized in that: this catalyst is applicable to the oxidation reaction of the unsaturated alcohol of 3-12 carbon atom, 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 more preferably applicable to 3-methyl-3-butenol and 3-methyl-2 butenol and be oxidized to the reaction of 3-methyl-3-crotonaldehyde and 3-methyl-2-butene aldehyde.
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN107812531A (en) * | 2017-10-19 | 2018-03-20 | 万华化学集团股份有限公司 | A kind of olefinic unsaturated alcohol prepares the catalyst of alkene unsaturated aldehyde, Its Preparation Method And Use |
| CN108014797A (en) * | 2017-12-08 | 2018-05-11 | 万华化学集团股份有限公司 | A kind of monatomic catalyst of supported silver for being used for unsaturated higher alcohols oxidation and preparation method thereof |
| CN108452799A (en) * | 2018-05-10 | 2018-08-28 | 北京化工大学 | A kind of preparation method of loading type silver catalyst and its application of catalytic phenylmethanol anaerobic dehydrogenation producing benzaldehyde |
| 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 |
| CN111229216A (en) * | 2018-11-29 | 2020-06-05 | 万华化学集团股份有限公司 | Eggshell type silver catalyst and preparation method and application thereof |
| CN114380677A (en) * | 2020-10-16 | 2022-04-22 | 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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| 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 |
| CN107812531A (en) * | 2017-10-19 | 2018-03-20 | 万华化学集团股份有限公司 | A kind of olefinic unsaturated alcohol prepares the catalyst of alkene unsaturated aldehyde, Its Preparation Method And Use |
| CN108014797A (en) * | 2017-12-08 | 2018-05-11 | 万华化学集团股份有限公司 | A kind of monatomic catalyst of supported silver for being used for unsaturated higher alcohols oxidation and preparation method 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 |
| CN108452799A (en) * | 2018-05-10 | 2018-08-28 | 北京化工大学 | A kind of preparation method of loading type silver catalyst and its application of catalytic phenylmethanol anaerobic dehydrogenation producing benzaldehyde |
| 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 |
| CN111229216A (en) * | 2018-11-29 | 2020-06-05 | 万华化学集团股份有限公司 | Eggshell type silver catalyst and preparation method and application thereof |
| 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 |
| CN114380677A (en) * | 2020-10-16 | 2022-04-22 | 万华化学集团股份有限公司 | Preparation method of 3-methyl-2-butenal |
| 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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