CN101507925B - Catalyst for selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol and preparation method thereof - Google Patents
Catalyst for selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing an unsaturated alcohol by the selective hydrogenation of an unsaturated aldehyde and a method for preparing the same. The catalyst consists of a carrier of rare-earth oxide and an active component of noble metal platinum, wherein the weight of the noble metal platinum is 0.6 to 5.1 percent of that of the rare-earth oxide. The catalyst can be prepared by the dipping method or precipitation-deposition method; the dipping method comprises that: a solution of platinum salt is added with the carrier of rare-earth oxide and the mixture is subjected to stirring, standing, water removal by heating, drying, high-temperature roasting, and reduction by hydrogen to prepare the catalyst; and the precipitation-deposition method comprises that: the solution of platinum salt is heated, added with an alkali solution to adjust the pH value, and added with the carrier of rare-earth oxide, and the mixture is subjected to stirring, washing, filtering, drying, high-temperature roasting, and reduction by hydrogen to prepare the catalyst. In the preparation of the catalyst, the solid phase catalytic reaction is adopted, and the unsaturated alcohol is synthesized by the elective hydrogenation of the unsaturated aldehyde, so that the activity and selectivity are higher, and the selectivity of the unsaturated alcohol reaches more than 80 percent.
Description
Technical field
The present invention relates to be used for the Catalysts and its preparation method of selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol.
Background technology
Unsaturated alcohol is extensive application in fine chemicals is synthetic, especially at flavor chemistry and pharmaceutical field.Usually unsaturated alcohol is obtained by the unsaturated aldehyde selective hydrogenation, but contain two functional groups of C=O and C=C in the unsaturated aldehyde molecule, and the bond energy of C=O key is greater than the C=C key, and the two has conjugation, makes reaction only select hydrogenation on the C=O key and do not destroy relatively difficulty of C=C key.Therefore seek high activity and the high-selectivity catalyst that the unsaturated aldehyde selective hydrogenation prepares unsaturated alcohol, have important reality and theory significance.
Au/TiO such as R.Zanella
2The catalyst crotonaldehyde selective hydrogenation is to the selectivity of crotonyl alcohol can reach about 65% (R.Zanella, et al., [J] .J.Catal., 2004,223 (2): 328-339.), and Pt/SnO such as K.Liberkov á
2The catalyst crotonaldehyde selective hydrogenation can reach about 70% (K.Liberkov á, R.Touroude, [J] .J.Mol.Catal.A, 2002,180 (1): 221-230) to the selectivity of crotonyl alcohol.
Mainly be to adopt reduction crotonaldehydes such as sodium borohydride, tetrahydro lithium aluminium or aluminium isopropoxide to obtain crotonyl alcohol at present, but have severe reaction conditions, product and reducing agent, separated from solvent difficulty, the post processing of product is loaded down with trivial details, shortcoming such as more than the three wastes of generation.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of catalytic activity height, good to the unsaturated alcohol selectivity, is used for the Catalysts and its preparation method of selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol.
For solving above technical problem, the technical solution used in the present invention is as follows:
The catalyst that is used for selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol, form by carrier and active component, it is characterized in that: described carrier is a rare-earth oxide, and active component is a noble metal platinum, and noble metal platinum weight is the 0.6%-5.1% of rare-earth oxide weight.
Described rare-earth oxide is yittrium oxide or praseodymium oxide.
The Preparation of catalysts method that is used for selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol can prepare with infusion process or deposition sedimentation method:
Use immersion process for preparing, comprise the steps:
(1) by platinum weight be the 0.6%-5.1% of rare-earth oxide weight, preparation platinum salting liquid adds carrier of rare-earth oxide in the solubility platinum salting liquid as the maceration extract that supports the noble metal active component, leaves standstill after stirring 0.5-12 hour;
(2) moisture content is removed in (1) heating, then at 100-150 degree centigrade of dry 5-12 hour, at last in high temperature furnace 300-650 degree centigrade obtained catalyst precursor in roasting 2-12 hour;
(3) obtain catalyst of the present invention after the activated processing of catalyst precursor that (2) are obtained.
With the preparation of deposition sedimentation method, comprise the steps:
(1) by platinum weight be the 0.6%-5.1% of rare-earth oxide weight, preparation platinum salting liquid dilutes with deionized water, be heated to 60-80 degree centigrade, adopt alkaline solution to regulate the pH value in the 6-10 scope, add carrier of rare-earth oxide, stirred 0.5-5 hour;
(2) the mixed liquor washing and filtering that (1) is obtained, then at 100-150 degree centigrade of dry 5-12 hour, at last in high temperature furnace 300-650 degree centigrade obtained catalyst precursor in roasting 2-12 hour;
(3) obtain catalyst of the present invention after the activated processing of catalyst precursor that (2) are obtained.
Described alkaline solution is ammoniacal liquor or sodium hydroxide solution or sodium carbonate liquor.
Above-mentioned activation processing be meant described catalyst precursor in hydrogen atmosphere 150-700 degree centigrade the reduction 1 hour.
Above-mentioned platinum salt is chloroplatinic acid or platinum nitrate.
The concentration of above-mentioned platinum salt is 10g/L.
Catalyst of the present invention adopts gas-solid catalysis, to selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol, has higher activity and selectivity, and the selectivity of unsaturated alcohol can reach more than 80%.In addition, catalyst of the present invention is used for the gas-solid phase reaction of selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol, and reaction condition is gentle relatively, and product separates easily with catalyst, and post processing is simple, and catalyst can be recycling, and the three wastes produce less.
The specific embodiment
Below in conjunction with embodiment the present invention is made further and to specify, but the present invention is not limited to these embodiment.
Embodiment 1
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 1.5ml chloroplatinic acid aqueous solution and add 1g carrier yittrium oxide, left standstill after stirring 0.5 hour, moisture content is removed in heating, and then 100 degrees centigrade of dryings 5 hours, 300 degrees centigrade of roastings 2 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 150 degrees centigrade of reduction obtain platinum/yittrium oxide catalyst after 1 hour, platinum weight is 0.6% of yittrium oxide weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 50 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table 1.
Embodiment 2
At first compound concentration is the platinum nitrate aqueous solution 100ml of 10g/L.Get the 1ml platinum nitrate aqueous solution and add 1g carrier yittrium oxide, left standstill after stirring 0.5 hour, moisture content is removed in heating, and then 120 degrees centigrade of dryings 8 hours, 500 degrees centigrade of roastings 6 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 500 degrees centigrade of reduction obtain platinum/yittrium oxide catalyst after 1 hour, platinum weight is 0.6% of yittrium oxide weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 80 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table 1.
Embodiment 3
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 1.5ml chloroplatinic acid aqueous solution and add 1g carrier yittrium oxide, left standstill after stirring 6 hours, moisture content is removed in heating, and then 150 degrees centigrade of dryings 8 hours, 500 degrees centigrade of roastings 6 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 700 degrees centigrade of reduction obtain platinum/yittrium oxide catalyst after 1 hour, platinum weight is 0.6% of yittrium oxide weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 120 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table 1.
Embodiment 4
At first compound concentration is the platinum nitrate aqueous solution 100ml of 10g/L.Get the 4ml platinum nitrate aqueous solution and add 1g carrier oxidation spectrum, left standstill after stirring 0.5 hour, moisture content is removed in heating, and then 100 degrees centigrade of dryings 5 hours, 300 degrees centigrade of roastings 2 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 150 degrees centigrade of reduction obtain platinum/oxidation spectrum catalyst after 1 hour, platinum weight is 2.4% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 50 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table 1.
Embodiment 5
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 6ml chloroplatinic acid aqueous solution and add 1g carrier oxidation spectrum, left standstill after stirring 6 hours, moisture content is removed in heating, and then 120 degrees centigrade of dryings 8 hours, 500 degrees centigrade of roastings 6 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 500 degrees centigrade of reduction obtain platinum/oxidation spectrum catalyst after 1 hour, platinum weight is 2.3% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 80 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table 1.
Embodiment 6
At first compound concentration is the platinum nitrate aqueous solution 100ml of 10g/L.Get the 4ml platinum nitrate aqueous solution and add 1g carrier oxidation spectrum, left standstill after stirring 12 hours, moisture content is removed in heating, and then 150 degrees centigrade of dryings 12 hours, 650 degrees centigrade of roastings 12 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 700 degrees centigrade of reduction obtain platinum/oxidation spectrum catalyst after 1 hour, platinum weight is 2.4% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 120 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table l.
Embodiment 7
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 13.5ml chloroplatinic acid aqueous solution and add 1g carrier yittrium oxide, left standstill after stirring 0.5 hour, moisture content is removed in heating, and then 100 degrees centigrade of dryings 5 hours, 300 degrees centigrade of roastings 2 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 150 degrees centigrade of reduction obtained platinum/yittrium oxide catalyst in back 1 hour, platinum weight is 5.1% of yittrium oxide weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 50 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table 1.
Embodiment 8
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 13.5ml chloroplatinic acid aqueous solution and add 1g carrier oxidation spectrum, left standstill after stirring 6 hours, moisture content is removed in heating, and then 120 degrees centigrade of dryings 8 hours, 650 degrees centigrade of roastings 6 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 500 degrees centigrade of reduction obtain platinum/oxidation spectrum catalyst after 1 hour, platinum weight is 5.1% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 80 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table 1.
Embodiment 9
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 13.5ml chloroplatinic acid aqueous solution and add 1g carrier oxidation spectrum, left standstill after stirring 12 hours, moisture content is removed in heating, and then 150 degrees centigrade of dryings 12 hours, 650 degrees centigrade of roastings 12 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 700 degrees centigrade of reduction obtain platinum/oxidation spectrum catalyst after 1 hour, platinum weight is 5.1% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction of methacrylaldehyde selective hydrogenation synthesizing propylene alcohol, and catalyst amount is 0.1 gram, and hydrogen/methacrylaldehyde mol ratio is 50: 1, and total flow is 26ml/min, and reaction temperature is 120 degrees centigrade.The conversion ratio of methacrylaldehyde and the selectivity of propenyl see Table 1.
Embodiment 10
At first compound concentration is the platinum nitrate aqueous solution 100ml of 10g/L.Get the 1ml platinum nitrate aqueous solution and be diluted to 100ml with deionized water, be heated to 60 degrees centigrade, adopt ammoniacal liquor to regulate pH value to 6, add 1g carrier oxidation spectrum, stirred 0.5 hour, washing and filtering is then 100 degrees centigrade of dryings 5 hours, 300 degrees centigrade of roastings 2 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 150 degrees centigrade of reduction obtain platinum/oxidation spectrum catalyst after 1 hour, platinum weight is 0.6% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 50 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
Embodiment 11
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 1.5ml chloroplatinic acid aqueous solution and be diluted to 100ml with deionized water, be heated to 70 degrees centigrade, adopt ammoniacal liquor to regulate pH value to 8, add 1g carrier yittrium oxide, stirred 3 hours, washing and filtering is then 120 degrees centigrade of dryings 8 hours, 500 degrees centigrade of roastings 6 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 500 degrees centigrade of reduction obtain platinum/yittrium oxide catalyst after 1 hour, platinum weight is 0.6% of yittrium oxide weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 80 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
Embodiment 12
At first compound concentration is the platinum nitrate aqueous solution 100ml of 10g/L.Get the 1ml platinum nitrate aqueous solution and be diluted to 100ml with deionized water, be heated to 80 degrees centigrade, adopt ammoniacal liquor to regulate pH value to 10, add 1g carrier yittrium oxide, stirred 5 hours, washing and filtering is then 150 degrees centigrade of dryings 12 hours, 650 degrees centigrade of roastings 12 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 700 degrees centigrade of reduction obtain platinum/yittrium oxide catalyst after 1 hour, platinum weight is 0.6% of yittrium oxide weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 120 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
Embodiment 13
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 6ml chloroplatinic acid aqueous solution and be diluted to 100ml with deionized water, be heated to 60 degrees centigrade, adopt sodium hydroxide solution to regulate pH value to 6, add 1g carrier oxidation spectrum, stirred 0.5 hour, washing and filtering is then 100 degrees centigrade of dryings 5 hours, 300 degrees centigrade of roastings 2 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 150 degrees centigrade of reduction obtain platinum/oxidation spectrum catalyst after 1 hour, platinum weight is 2.3% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 50 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
Embodiment 14
At first compound concentration is the platinum nitrate aqueous solution 100ml of 10g/L.Get the 4ml platinum nitrate aqueous solution and be diluted to 100ml with deionized water, be heated to 70 degrees centigrade, adopt sodium hydroxide solution to regulate pH value to 8, add 1g carrier praseodymium oxide, stirred 3 hours, washing and filtering is then 120 degrees centigrade of dryings 8 hours, 500 degrees centigrade of roastings 6 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 500 degrees centigrade of reduction obtain platinum/oxidation spectrum catalyst after 1 hour, platinum weight is 2.4% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 80 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
Embodiment 15
At first compound concentration is the platinum nitrate aqueous solution 100ml of 10g/L.Get the 4ml platinum nitrate aqueous solution and be diluted to 100ml with deionized water, be heated to 80 degrees centigrade, adopt sodium hydroxide solution to regulate pH value to 10, add 1g carrier yittrium oxide, stirred 5 hours, washing and filtering is then 150 degrees centigrade of dryings 12 hours, 650 degrees centigrade of roastings 12 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 700 degrees centigrade of reduction obtain platinum/yittrium oxide catalyst after 1 hour, platinum weight is 2.4% of yittrium oxide weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 120 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
Embodiment 16
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 13.5ml chloroplatinic acid aqueous solution and be diluted to 100ml with deionized water, be heated to 60 degrees centigrade, adopt sodium carbonate liquor to regulate pH value to 6, add 1g carrier yittrium oxide, stirred 0.5 hour, washing and filtering is then 100 degrees centigrade of dryings 5 hours, 300 degrees centigrade of roastings 2 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 150 degrees centigrade of reduction obtain platinum/yittrium oxide catalyst after 1 hour, platinum weight is 5.1% of yittrium oxide weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 50 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
Embodiment 17
At first compound concentration is the platinum nitrate aqueous solution 100ml of 10g/L.Get the 8ml platinum nitrate aqueous solution and be diluted to 100ml with deionized water, be heated to 70 degrees centigrade, adopt sodium carbonate liquor to regulate pH value to 8, add 1g carrier praseodymium oxide, stirred 3 hours, washing and filtering is then 120 degrees centigrade of dryings 8 hours, 500 degrees centigrade of roastings 6 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 500 degrees centigrade of reduction obtain platinum/praseodymium oxide catalyst after 1 hour, platinum weight is 4.9% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 80 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
Embodiment 18
At first compound concentration is the chloroplatinic acid aqueous solution 100ml of 10g/L.Get the 13.5ml chloroplatinic acid aqueous solution and be diluted to 100ml with deionized water, be heated to 80 degrees centigrade, adopt sodium carbonate liquor to regulate pH value to 10, add 1g carrier oxidation spectrum, stirred 5 hours, washing and filtering is then 150 degrees centigrade of dryings 12 hours, 650 degrees centigrade of roastings 12 hours in high temperature furnace at last obtain catalyst precursor.Catalyst precursor is at H
2In 700 degrees centigrade of reduction obtain platinum/praseodymium oxide catalyst after 1 hour, platinum weight is 5.1% of oxidation spectrum weight in the catalyst.The catalyst that makes is applied to the gas-solid phase reaction that crotonaldehyde selective hydrogenation synthesizes crotonyl alcohol, and catalyst amount is 0.1 gram, and hydrogen/crotonaldehyde mol ratio is 94: 1, and total flow is 26ml/min, and reaction temperature is 120 degrees centigrade.The conversion ratio of crotonaldehyde and the selectivity of crotonyl alcohol see Table 1.
The conversion ratio of the unsaturated aldehyde among the table 1. embodiment 1-18 on the loaded platinum catalyst and the selectivity of unsaturated alcohol
From table, can analyze and draw, catalyst of the present invention is used for the gas-phase reaction of unsaturated aldehyde selective hydrogenation to prepare unsaturated alcohol, the content of Pt and reaction temperature are bigger to the catalytic activity influence, and along with the increase of Pt content and the raising of reaction temperature, activity of such catalysts all improves.The weight of platinum is 5.1% o'clock of oxidation spectrum weight, and platinum/yittrium oxide catalyst has best choice to propenyl when 50 ℃ of reactions, can reach 77.5%.The weight of platinum is 5.1% o'clock of oxidation spectrum weight, and platinum/oxidation spectrum catalyst has best choice to crotonyl alcohol, can reach 84.8% when 50 ℃ of reactions.
Claims (2)
1. be used for the Preparation of catalysts method of selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol, it is characterized in that: utilize immersion process for preparing, comprise the steps:
(1) by platinum weight be the 0.6%-5.1% of praseodymium oxide weight, preparation platinum salting liquid adds the praseodymium oxide carrier, leaves standstill after stirring 0.5-12 hour, and described platinum salt is chloroplatinic acid or platinum nitrate;
(2) moisture content is removed in (1) heating, then at 100-150 degree centigrade of dry 5-12 hour, at last in high temperature furnace 300-650 degree centigrade obtained catalyst precursor in roasting 2-12 hour;
(3) obtain catalyst after the activated processing of catalyst precursor that (2) are obtained; Described activation processing be described catalyst precursor in hydrogen atmosphere 150-700 degree centigrade the reduction 1 hour.
2. be used for the Preparation of catalysts method of selectively hydrogenizing unsaturated aldehyde into unsaturated alcohol, it is characterized in that: utilize the preparation of deposition sedimentation method, comprise the steps:
(1) by platinum weight be the 0.6%-5.1% of praseodymium oxide weight, preparation platinum salting liquid with the deionized water dilution, is heated to 60-80 degree centigrade, adopts alkaline solution to regulate the pH value in the 6-10 scope, adds the praseodymium oxide carrier, stirs 0.5-5 hour; Described platinum salt is chloroplatinic acid or platinum nitrate; Described alkaline solution is ammoniacal liquor or sodium hydroxide solution or sodium carbonate liquor;
(2) the mixed liquor washing and filtering that (1) is obtained, then at 100-150 degree centigrade of dry 5-12 hour, at last in high temperature furnace 300-650 degree centigrade obtained catalyst precursor in roasting 2-12 hour;
(3) obtain catalyst after the activated processing of catalyst precursor that (2) are obtained, described activation processing be described catalyst precursor in hydrogen atmosphere 150-700 degree centigrade the reduction 1 hour.
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