CN102614914B - Catalyst for synthesizing ethanol by acetic acid hydrogenation, preparation method and application thereof - Google Patents
Catalyst for synthesizing ethanol by acetic acid hydrogenation, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing ethanol by acetic acid hydrogenation. The catalyst consists of 0.3 to 0.5 weight percent of Pt, 0.02 to 2.8 weight percent of Ag, 0 to 0.5 weight percent of metal aid and the balance of carrier. The catalyst has the advantages of low cost, high activity and high selectivity of ethanol.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method and application of synthesizing alcohol, is a kind of catalyst and preparation method and application of acetic acid hydrogenation synthesizing alcohol specifically.
Technical background
Ethanol is not only good fuel, and is good fuel additive.Ethanol is good Gasoline oxygenate and octane number blend component, can replace methyl tertiary butyl ether(MTBE) (MTBE) or ethyl tert-butyl ether (ETBE) (ETBE), can reduce tail gas CO discharge.The industrial process of alcohol fuel is mainly grain and industrial crops fermentation method at present.The raw material of China's fuel ethanol production is mainly corn and wheat, and not only cost is high but also serious threat national food safety.
Non-grain route method ethanol production is subject to increasing attention, and patent CN101235392, CN101289677 have reported take the alcohol production technology that cellulose is raw material.Cellulose fermentation is produced the ethanol technology and has been overcome the problem that the grain fermentation method occupies cultivated land, but, because the factors such as the cellulase cost is high, the cellulose energy density is low cause the cellulosic ethanol production cost high, makes the industrialization development of this technology be restricted.Patent CN1225852 has reported that, from the technology of synthesis gas one-step synthesis ethanol, this process is subject to the ASF distribution limitation, and ethanol is selectively lower.United States Patent (USP) U.S. Pat. No. 2,607,807, U.S. Pat. No. 4,517,391, U.S. Pat. No. 5,149,680, CN102149661, CN102271805 have reported catalyst and the application thereof of acetic acid hydrogenation synthesizing alcohol, it is simple that the acetic acid hydrogenation technique has flow process, characteristics easy and simple to handle.In the patent of these reports, patent U.S. Pat. No. 2,607,807 operating pressures too high (70MPa), patent U.S. Pat. No. 5,149,680 poor selectivity (alkane of 3-9%), patent U.S. Pat. No. 4,517,391 cobalt loadings very high (surpassing 50%), these unfavorable factors have limited the industrial applications of above catalyst.Patent US Pat. No. 7,863,489, CN102149661, CN102271805 have reported the application of supported Pt catalysts in the acetic acid hydrogenation, demonstrate catalytic performance preferably, and Pt load capacity still is higher (0.5-1.0wt%) still.
Summary of the invention
The objective of the invention is for current acetic acid hydrogenation catalyst noble-metal-supported amount highly, cost is high, and the shortcoming of poor selectivity provides catalyst and the preparation method and application of the selective high acetic acid hydrogenation synthesizing alcohol of a kind of high, ethanol with low cost, active.
Catalyst of the present invention consists of:
Pt load capacity 0.3-0.5wt%, Ag load capacity 0.02-2.8wt%, the load capacity of metal promoter is 0-0.5wt%, surplus is carrier.
Metal promoter as above is one or more of Mo, Sn, Co, W, Cr, Mn, Fe, Ni, Cu, Zn, Ru, Rh, Pd, La, Ce, Th.
Carrier as above is alundum (Al2O3), molecular sieve, silica, titanium dioxide, zirconia or diatomite etc.
The key of Pt catalyst preparation technology is the high degree of dispersion of Pt on carrier, and the Pt method for preparing catalyst adopts conventional equi-volume impregnating substantially at present, and the dispersion of Pt on carrier is difficult to control.This is mainly manifested in two aspects: one, the defective bit of carrier surface absorption Pt is limited, and while causing flooding, Pt is difficult to high degree of dispersion on carrier; Two, metal agglomeration easily occurs in the catalyst precursor of supporting Pt compound when high-temperature roasting.Because the Pt dispersiveness is low, reach the requirement of industrializeding catalyst, the Pt load capacity need reach certain value, and this has just caused the increase of catalyst cost.Reduce the Pt load capacity and will deposit above two aspects improvement method for preparing catalyst.At first, catalyst surface is carried out to the organo-functional group modification, make its surface form the adsorption potential of absorption Pt compound.Secondly, the Pt loaded on carrier is carried out to Alloying Treatment, reduce its sintering degree in roasting process.
The preparation method of catalyst provided by the invention comprises the following steps:
(1) by the APTES(3-aminopropyl triethoxysilane) join in ethanolic solution and be made into the APTES ethanolic solution, carrier is joined in the APTES ethanolic solution again, APTES wherein: ethanol: carrier=10-15 g:100-150 ml:10-20 g, by the mixture 18-30 hour that refluxes, mixture after backflow is with after the ethanol washing, at 60-80 ℃ of dry 2-5 hour, obtain the carrier after the APTES modification;
(2) platinum acid chloride solution that compound concentration is 0.0086-0.0382 mol/L, on carrier by the platinum acid chloride solution incipient impregnation after step (1) APTES modification, wherein, carrier after the APTES modification: platinum acid chloride solution=10-20 g:10-30 ml, carrier after the load chloroplatinic acid is at room temperature placed 2-5 hour, obtain sample 1 after dry 6-12 hour again under 100-120 ℃, sample 1 is joined in the solution of potassium borohydride of 0.2-0.4 M and stir reductase 12 0-60 min, wherein, sample 1: solution of potassium borohydride=10-20 g:20-40 ml, afterwards sample 1 is at room temperature placed to 2-5 hour, dry 6-12 hour under 100-120 ℃ again, obtain supporting Pt carrier afterwards,
(3) liquor argenti nitratis ophthalmicus of preparation 0.0007-0.4830 mol/L, on carrier by the liquor argenti nitratis ophthalmicus incipient impregnation after step (2) supporting Pt, wherein, carrier after supporting Pt: liquor argenti nitratis ophthalmicus=10-20 g:10-30 ml, carrier after the load silver nitrate is at room temperature placed 2-5 hour, obtain sample 2 after dry 6-12 hour again under 100-120 ℃, sample 2 is joined in the solution of potassium borohydride of 0.2-0.4 M and stir reductase 12 0-60 min, wherein, sample 2: solution of potassium borohydride=5-10 g:20-40 ml, afterwards sample is at room temperature placed to 2-5 hour, dry 6-12 hour under 100-120 ℃ again, obtain the catalyst without metal promoter,
(4) for the metal promoter load capacity > preparation of the catalyst of 0wt%, solubility is joined in deionized water containing auxiliary compound, be mixed with the metal promoter solution of 0.0008-0.0811 mol/L, by metal promoter solution incipient impregnation in step (3) catalyst without metal promoter, wherein, catalyst without metal promoter: metal promoter solution=10-20 g:10-30 ml, the catalyst of carried metal auxiliary compound is at room temperature placed to 2-5 hour, dry 6-12 hour under 100-120 ℃ again, roasting 3-6 hour in 400-600 ℃ of air, obtain the catalyst of containing metal auxiliary agent.
All kinds of Pt-Ag catalyst as above can be applicable in fixed-bed tube reactor.Concrete reducing condition is as follows: by catalyst at H
2under atmosphere, with the heating rate of 0.5-3 ℃/min, be elevated to 400-600 ℃ of reduction 3-8 hour, H
2gas space velocity GHSV=1500-9000 h
-1.Reaction condition is: in reaction temperature 200-300 ℃ of scope, reaction pressure is at 1.0-3.0 MPa, acetic acid liquid air speed LHSV=0.5-3 h
-1, H
2: the acetic acid mol ratio is 5-50.
Under reaction condition as mentioned above, the acetic acid conversion ratio is greater than 90%, and ethanol selectively is greater than 85%.
The present invention's advantage compared with prior art:
1, support type Pt-Ag catalyst provided by the invention use APTES as the modifier of carrier surface functionalization, Ag as with Pt, forming the metal of alloy.
2, method for preparing catalyst noble-metal-supported amount provided by the invention is low, and production cost is low.
3, catalyst of the present invention is applied to acetic acid hydrogenation synthesizing alcohol reaction condition gentleness, and the acetic acid conversion ratio is high, ethanol is selective high, catalyst stability is good.
4, product ethanol, acetaldehyde, ethyl acetate are high value added product, and hydrocarbon product content is extremely low.
The specific embodiment
Below provide several illustrative rather than restrictive example:
Embodiment 1:
15 g APTES are joined in 100 ml ethanol, be mixed with solution.12 g silica are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 18 hours.Mixture after backflow is with after ethanol washing, 75 ℃ of dryings 4 hours, obtains the silica after the APTES modification.Platinum acid chloride solution 20 ml that compound concentration is 0.0131 mol/L, on the silica by the platinum acid chloride solution incipient impregnation after the APTES modification.Silica after the load chloroplatinic acid is at room temperature placed 2 hours, then under 120 ℃ dry 11 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 30 ml 0.4 M, stir reductase 12 0 min, filter afterwards, wash away chlorion, at room temperature place 3 hours, then under 110 ℃ dry 6 hours, obtain the silica after supporting Pt.Liquor argenti nitratis ophthalmicus 20 ml that compound concentration is 0.0564 mol/L, on the silica by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 3 hours, then under 100 ℃ dry 8 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 20 ml 0.25 M, stirred reduction 35 min, wash afterwards, filter, at room temperature place 5 hours, under 110 ℃, drying is 11 hours, obtains the catalyst without metal promoter.Above-mentioned Pt-Ag catalyst Pt quality percentage composition is 0.32wt%, and Ag quality percentage composition is 0.5wt%, and silica quality percentage composition is 98.58 wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: catalyst is at H
2heating rate with 2 ℃/min under atmosphere is elevated to 450 ℃ of reduction 3 hours, H
2gas space velocity GHSV=4500 h
-1.200 ℃ of reaction temperatures, reaction pressure is at 2.5 MPa, acetic acid liquid air speed LHSV=1 h
-1, H
2: the acetic acid mol ratio is 5.Under reaction condition as mentioned above, acetic acid conversion ratio 96.5%, ethanol selective 86.5%.
Embodiment 2:
15 g APTES are joined in 100 ml ethanol, be mixed with solution.12 g silica are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 26 hours.Mixture after backflow is with after ethanol washing, 70 ℃ of dryings 5 hours, obtains the silica after the APTES modification.Platinum acid chloride solution 20 ml that compound concentration is 0.0100 mol/L, on the silica by the platinum acid chloride solution incipient impregnation after the APTES modification.Silica after the load chloroplatinic acid is at room temperature placed 4 hours, then under 110 ℃ dry 12 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 30 ml 0.3 M, stir reduction 40 min, filter afterwards, wash away chlorion, at room temperature place 2 hours, then under 100 ℃ dry 9 hours, obtain the silica after supporting Pt.Liquor argenti nitratis ophthalmicus 20 ml that compound concentration is 0.0281 mol/L, on the silica by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 2 hours, then under 120 ℃ dry 12 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 20 ml 0.35 M, stirred reduction 45 min, wash afterwards, filter, at room temperature place 3 hours, under 110 ℃, drying is 10 hours, obtains the catalyst without metal promoter.Manganese nitrate solution 20 ml that compound concentration is 0.0276 mol/L, the manganese nitrate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 3 hours, and under 120 ℃, drying is 10 hours, in 400 ℃ of air, roasting is 4 hours, obtains the Pt-Ag-Mn catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.32wt%, and Ag quality percentage composition is 0.5wt%, and Mn quality percentage composition is 0.25wt%, and silica quality percentage composition is 98.93wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: catalyst is at H
2heating rate with 0.5 ℃/min under atmosphere is elevated to 400 ℃ of reduction 7 hours, H
2gas space velocity GHSV=1500 h
-1.250 ℃ of reaction temperatures, reaction pressure is at 1 MPa, acetic acid liquid air speed LHSV=3 h
-1, H
2: the acetic acid mol ratio is 50.Under reaction condition as mentioned above, acetic acid conversion ratio 98.3%, ethanol selective 95.5%.
Embodiment 3:
12 g APTES are joined in 130 ml ethanol, be mixed with solution.18 g alundum (Al2O3)s are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 24 hours.Mixture after backflow is with after ethanol washing, 70 ℃ of dryings 3 hours, obtains the alundum (Al2O3) after the APTES modification.Platinum acid chloride solution 10 ml that compound concentration is 0.0354 mol/L, on the alundum (Al2O3) by the platinum acid chloride solution incipient impregnation after the APTES modification.Alundum (Al2O3) after the load chloroplatinic acid is at room temperature placed 3 hours, then under 100 ℃ dry 8 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 20 ml 0.35 M, stir reduction 55 min, filter afterwards, wash away chlorion, at room temperature place 4 hours, then under 120 ℃ dry 8 hours, obtain the alundum (Al2O3) after supporting Pt.Liquor argenti nitratis ophthalmicus 10 ml that compound concentration is 0.0084 mol/L, on the alundum (Al2O3) by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 5 hours, then under 110 ℃ dry 11 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 25 ml 0.3 M, stirred reduction 40 min, wash afterwards, filter, at room temperature place 2 hours, under 100 ℃, drying is 8 hours, obtains the catalyst without metal promoter.Iron nitrate solution 10 ml that compound concentration is 0.1622 mol/L, the iron nitrate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 2 hours, and under 110 ℃, drying is 8 hours, in 550 ℃ of air, roasting is 6 hours, obtains the Pt-Ag-Fe catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.38wt%, and Ag quality percentage composition is 0.05wt%, and Fe quality percentage composition is 0.5wt%, and alundum (Al2O3) quality percentage composition is 99.07wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 1 ℃/min under atmosphere is elevated to 550 ℃, and at this temperature, reduction is 6 hours, H
2gas space velocity GHSV=6000 h
-1.230 ℃ of reaction temperatures, reaction pressure is at 1.5MPa, acetic acid liquid air speed LHSV=1 h
-1, H
2: the acetic acid mol ratio is 10.Under reaction condition as mentioned above, acetic acid conversion ratio 90.5%, ethanol selective 92.4%.
Embodiment 4:
10 g APTES are joined in 150 ml ethanol, be mixed with solution.10 g titanium dioxide are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 24 hours.Mixture after backflow is with after ethanol washing, 65 ℃ of dryings 4 hours, obtains the titanium dioxide after the APTES modification.Platinum acid chloride solution 10 ml that compound concentration is 0.0258 mol/L, on the titanium dioxide by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 5 hours, then under 110 ℃ dry 7 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 25 ml 0.35 M, stir reduction 60 min, filter afterwards, wash away chlorion, at room temperature place 5 hours, then under 110 ℃ dry 7 hours, obtain the titanium dioxide after supporting Pt.Liquor argenti nitratis ophthalmicus 10 ml that compound concentration is 0.0019 mol/L, on the titanium dioxide by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 2 hours, then under 100 ℃ dry 7 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 40 ml 0.2 M, stirred reductase 12 0 min, wash afterwards, filter, at room temperature place 3 hours, under 120 ℃, drying is 9 hours, obtains the catalyst without metal promoter.Stannous chloride solution 10 ml that compound concentration is 0.0085 mol/L, stannous chloride solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 2 hours, and under 110 ℃, drying is 11 hours, in 600 ℃ of air, roasting is 6 hours, obtains the Pt-Ag-Sn catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.5wt%, and Ag quality percentage composition is 0.02wt%, and Sn quality percentage composition is 0.1wt%, and titanium dioxide quality percentage composition is 99.38wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 1 ℃/min under atmosphere is elevated to 600 ℃, and at this temperature, reduction is 4 hours, H
2gas space velocity GHSV=6000 h
-1.240 ℃ of reaction temperatures, reaction pressure is at 3MPa, acetic acid liquid air speed LHSV=0.5 h
-1, H
2: the acetic acid mol ratio is 45.Under reaction condition as mentioned above, acetic acid conversion ratio 100%, ethanol selective 90.5%.
Embodiment 5:
10 g APTES are joined in 150 ml ethanol, be mixed with solution.16 g zirconias are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 18 hours.Mixture after backflow is with after ethanol washing, 65 ℃ of dryings 3 hours, obtains the zirconia after the APTES modification.Platinum acid chloride solution 25 ml that compound concentration is 0.0113 mol/L, on the zirconia by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 2 hours, then under 120 ℃ dry 6 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 25 ml 0.25 M, stir reductase 12 5 min, filter afterwards, wash away chlorion, at room temperature place 3 hours, then under 120 ℃ dry 11 hours, obtain the zirconia after supporting Pt.Liquor argenti nitratis ophthalmicus 25 ml that compound concentration is 0.0060 mol/L, on the zirconia by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 5 hours, then under 110 ℃ dry 8 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 40 ml 0.25 M, stirred reduction 50 min, wash afterwards, filter, at room temperature place 5 hours, under 120 ℃, drying is 7 hours, obtains the catalyst without metal promoter.Chromium nitrate solution 25 ml that compound concentration is 0.0621 mol/L, the chromium nitrate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 5 hours, and under 100 ℃, drying is 7 hours, in 400 ℃ of air, roasting is 5 hours, obtains the Pt-Ag-Cr catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.34wt%, and Ag quality percentage composition is 0.1wt%, and Cr quality percentage composition is 0.5wt%, and zirconia quality percentage composition is 99.06wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 3 ℃/min under atmosphere is elevated to 600 ℃, and at this temperature, reduction is 5 hours, H
2gas space velocity GHSV=7500 h
-1.280 ℃ of reaction temperatures, reaction pressure is at 2.5MPa, acetic acid liquid air speed LHSV=0.5 h
-1, H
2: the acetic acid mol ratio is 30.Under reaction condition as mentioned above, acetic acid conversion ratio 90.5%, ethanol selective 96.3%.
Embodiment 6:
13 g APTES are joined in 120 ml ethanol, be mixed with solution.20 g diatomite are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 22 hours.Mixture after backflow is with after ethanol washing, 60 ℃ of dryings 2 hours, obtains the diatomite after the APTES modification.Platinum acid chloride solution 30 ml that compound concentration is 0.0155 mol/L, on the diatomite by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 5 hours, then under 100 ℃ dry 7 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 35 ml 0.2 M, stir reduction 60 min, filter afterwards, wash away chlorion, at room temperature place 2 hours, then under 120 ℃ dry 12 hours, obtain the diatomite after supporting Pt.Liquor argenti nitratis ophthalmicus 30 ml that compound concentration is 0.1530 mol/L, on the diatomite by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 3 hours, then under 120 ℃ dry 9 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 30 ml 0.3 M, stirred reductase 12 5 min, wash afterwards, filter, at room temperature place 2 hours, under 100 ℃, drying is 8 hours, obtains the catalyst without metal promoter.Zinc nitrate solution 30 ml that compound concentration is 0.0371 mol/L, the zinc nitrate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 2 hours, and under 120 ℃, drying is 12 hours, in 400 ℃ of air, roasting is 4 hours, obtains the Pt-Ag-Zn catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.44wt%, and Ag quality percentage composition is 2.4wt%, and Zn quality percentage composition is 0.35wt%, and diatomite quality percentage composition is 96.81wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 1.5 ℃/min under atmosphere is elevated to 400 ℃, and at this temperature, reduction is 5 hours, H
2gas space velocity GHSV=3000 h
-1.260 ℃ of reaction temperatures, reaction pressure is at 3MPa, acetic acid liquid air speed LHSV=1.5 h
-1, H
2: the acetic acid mol ratio is 20.Under reaction condition as mentioned above, acetic acid conversion ratio 90.7%, ethanol selective 85.2%.
Embodiment 7:
15 g APTES are joined in 100 ml ethanol, be mixed with solution.12 g silica are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 22 hours.Mixture after backflow is with after ethanol washing, 65 ℃ of dryings 5 hours, obtains the silica after the APTES modification.Platinum acid chloride solution 20 ml that compound concentration is 0.0151 mol/L, on the silica by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 3 hours, then under 110 ℃ dry 6 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 30 ml 0.3 M, stir reduction 55 min, filter afterwards, wash away chlorion, at room temperature place 5 hours, then under 100 ℃ dry 6 hours, obtain the silica after supporting Pt.Liquor argenti nitratis ophthalmicus 20 ml that compound concentration is 0.0854 mol/L, on the silica by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 4 hours, then under 100 ℃ dry 6 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 20 ml 0.2 M, stirred reduction 45 min, wash afterwards, filter, at room temperature place 4 hours, under 110 ℃, drying is 12 hours, obtains the catalyst without metal promoter.Ruthenium trichloride solution 20 ml that compound concentration is 0.0243 mol/L, ruthenium trichloride solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 4 hours, and under 120 ℃, drying is 10 hours, in 600 ℃ of air, roasting is 3 hours, obtains the Pt-Ag-Ru catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.48wt%, and Ag quality percentage composition is 1.5wt%, and Ru quality percentage composition is 0.4wt%, and silica quality percentage composition is 97.62wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 0.5 ℃/min under atmosphere is elevated to 400 ℃, and at this temperature, reduction is 6 hours, H
2gas space velocity GHSV=1500 h
-1.240 ℃ of reaction temperatures, reaction pressure is at 1MPa, acetic acid liquid air speed LHSV=0.5 h
-1, H
2: the acetic acid mol ratio is 50.Under reaction condition as mentioned above, acetic acid conversion ratio 92.1%, ethanol selective 94.8%.
Embodiment 8:
15 g APTES are joined in 100 ml ethanol, be mixed with solution.12 g silica are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 28 hours.Mixture after backflow is with after ethanol washing, 60 ℃ of dryings 2 hours, obtains the silica after the APTES modification.Platinum acid chloride solution 20 ml that compound concentration is 0.0093 mol/L, on the silica by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 2 hours, then under 110 ℃ dry 10 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 30 ml 0.25 M, stir reduction 30 min, filter afterwards, wash away chlorion, at room temperature place 2 hours, then under 110 ℃ dry 9 hours, obtain the silica after supporting Pt.Liquor argenti nitratis ophthalmicus 20 ml that compound concentration is 0.0045 mol/L, on the silica by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 3 hours, then under 110 ℃ dry 10 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 20 ml 0.25 M, stirred reduction 50 min, wash afterwards, filter, at room temperature place 2 hours, under 110 ℃, drying is 6 hours, obtains the catalyst without metal promoter.Preparation rhodium chloride concentration is mixed solution 20 ml that 0.0029 mol/L and lanthanum nitrate concentration are 0.0146 mol/L, by above-mentioned solution incipient impregnation on the catalyst without metal promoter, at room temperature place 4 hours, under 110 ℃, drying is 6 hours, in 450 ℃ of air, roasting is 6 hours, obtains the Pt-Ag-Rh catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.3wt%, and Ag quality percentage composition is 0.08wt%, and Rh quality percentage composition is 0.05wt%, and La quality percentage composition is 0.2wt%, and silica quality percentage composition is 99.37wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 1.5 ℃/min under atmosphere is elevated to 450 ℃, and at this temperature, reduction is 8 hours, H
2gas space velocity GHSV=9000 h
-1.210 ℃ of reaction temperatures, reaction pressure is at 1MPa, acetic acid liquid air speed LHSV=2.5 h
-1, H
2: the acetic acid mol ratio is 45.Under reaction condition as mentioned above, acetic acid conversion ratio 96.4%, ethanol selective 87.8%.
Embodiment 9:
12 g APTES are joined in 130 ml ethanol, be mixed with solution.18 g alundum (Al2O3)s are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 30 hours.Mixture after backflow is with after ethanol washing, 75 ℃ of dryings 5 hours, obtains the alundum (Al2O3) after the APTES modification.Platinum acid chloride solution 10 ml that compound concentration is 0.0382 mol/L, on the alundum (Al2O3) by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 3 hours, then under 100 ℃ dry 9 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 20 ml 0.2 M, stir reduction 50 min, filter afterwards, wash away chlorion, at room temperature place 3 hours, then under 110 ℃ dry 10 hours, obtain the alundum (Al2O3) after supporting Pt.Liquor argenti nitratis ophthalmicus 10 ml that compound concentration is 0.4830 mol/L, on the alundum (Al2O3) by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 2 hours, then under 120 ℃ dry 7 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 25 ml 0.35 M, stirred reduction 30 min, wash afterwards, filter, at room temperature place 3 hours, under 120 ℃, drying is 7 hours, obtains the catalyst without metal promoter.Palladium chloride solution 10 ml that compound concentration is 0.0316 mol/L, the palladium chloride solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 5 hours, and under 100 ℃, drying is 8 hours, in 500 ℃ of air, roasting is 4 hours, obtains the Pt-Ag-Pd catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.4wt%, and Ag quality percentage composition is 2.8wt%, and Pd quality percentage composition is 0.18wt%, and alundum (Al2O3) quality percentage composition is 96.62wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 2.5 ℃/min under atmosphere is elevated to 550 ℃, and at this temperature, reduction is 4 hours, H
2gas space velocity GHSV=3000 h
-1.260 ℃ of reaction temperatures, reaction pressure is at 2MPa, acetic acid liquid air speed LHSV=3 h
-1, H
2: the acetic acid mol ratio is 40.Under reaction condition as mentioned above, acetic acid conversion ratio 92.3%, ethanol selective 89.7%.
Embodiment 10:
14 g APTES are joined in 140 ml ethanol, be mixed with solution.10 g titanium dioxide are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 28 hours.Mixture after backflow is with after ethanol washing, 80 ℃ of dryings 5 hours, obtains the titanium dioxide after the APTES modification.Platinum acid chloride solution 10 ml that compound concentration is 0.0239 mol/L, on the titanium dioxide by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 4 hours, then under 100 ℃ dry 8 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 40 ml 0.3 M, stir reduction 45 min, filter afterwards, wash away chlorion, at room temperature place 5 hours, then under 100 ℃ dry 10 hours, obtain the titanium dioxide after supporting Pt.Liquor argenti nitratis ophthalmicus 10 ml that compound concentration is 0.0468 mol/L, on the titanium dioxide by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 5 hours, then under 100 ℃ dry 6 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 25 ml 0.35 M, stirred reduction 45 min, wash afterwards, filter, at room temperature place 3 hours, under 100 ℃, drying is 9 hours, obtains the catalyst without metal promoter.Lanthanum nitrate hexahydrate 10 ml that compound concentration is 0.0146 mol/L, the lanthanum nitrate hexahydrate incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 3 hours, and under 120 ℃, drying is 9 hours, in 500 ℃ of air, roasting is 3 hours, obtains the Pt-Ag-La catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.46wt%, and Ag quality percentage composition is 0.5wt%, and La quality percentage composition is 0.2wt%, and titanium dioxide quality percentage composition is 98.84wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 3 ℃/min under atmosphere is elevated to 500 ℃, and at this temperature, reduction is 7 hours, H
2gas space velocity GHSV=9000 h
-1.270 ℃ of reaction temperatures, reaction pressure is at 3 MPa, acetic acid liquid air speed LHSV=0.5 h
-1, H
2: the acetic acid mol ratio is 50.Under reaction condition as mentioned above, acetic acid conversion ratio 100%, ethanol selective 93.5%.
Embodiment 11:
10 g APTES are joined in 150 ml ethanol, be mixed with solution.16 g zirconias are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 26 hours.Mixture after backflow is with after ethanol washing, 75 ℃ of dryings 2 hours, obtains the zirconia after the APTES modification.Platinum acid chloride solution 25 ml that compound concentration is 0.0118 mol/L, on the zirconia by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 4 hours, then under 110 ℃ dry 10 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 25 ml 0.35 M, stir reduction 35 min, filter afterwards, wash away chlorion, at room temperature place 4 hours, then under 100 ℃ dry 8 hours, obtain the zirconia after supporting Pt.Liquor argenti nitratis ophthalmicus 25 ml that compound concentration is 0.1219 mol/L, on the zirconia by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 3 hours, then under 120 ℃ dry 8 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 40 ml 0.3 M, stirred reduction 35 min, wash afterwards, filter, at room temperature place 2 hours, under 110 ℃, drying is 9 hours, obtains the catalyst without metal promoter.Cerous nitrate solution 25 ml that compound concentration is 0.0212 mol/L, the cerous nitrate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 2 hours, and under 110 ℃, drying is 7 hours, in 450 ℃ of air, roasting is 5 hours, obtains the Pt-Ag-Ce catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.35wt%, and Ag quality percentage composition is 2wt%, and Ce quality percentage composition is 0.45wt%, and zirconia quality percentage composition is 97.2wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 2 ℃/min under atmosphere is elevated to 450 ℃, and at this temperature, reduction is 8 hours, H
2gas space velocity GHSV=4500 h
-1.220 ℃ of reaction temperatures, reaction pressure is at 1.5MPa, acetic acid liquid air speed LHSV=2 h
-1, H
2: the acetic acid mol ratio is 30.Under reaction condition as mentioned above, acetic acid conversion ratio 92.5%, ethanol selective 88.4%.
Embodiment 12:
13 g APTES are joined in 120 ml ethanol, be mixed with solution.20 g diatomite are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 20 hours.Mixture after backflow is with after ethanol washing, 70 ℃ of dryings 4 hours, obtains the diatomite after the APTES modification.Platinum acid chloride solution 30 ml that compound concentration is 0.0172 mol/L, on the diatomite by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 5 hours, then under 120 ℃ dry 9 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 35 ml 0.25 M, stir reduction 40 min, filter afterwards, wash away chlorion, at room temperature place 4 hours, then under 100 ℃ dry 7 hours, obtain the diatomite after supporting Pt.Liquor argenti nitratis ophthalmicus 30 ml that compound concentration is 0.0125 mol/L, on the diatomite by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 3 hours, then under 100 ℃ dry 11 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 30 ml 0.4 M, stirred reduction 40 min, wash afterwards, filter, at room temperature place 5 hours, under 120 ℃, drying is 10 hours, obtains the catalyst without metal promoter.Thorium nitrate solution 30 ml that compound concentration is 0.0043 mol/L, thorium nitrate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 3 hours, and under 120 ℃, drying is 6 hours, in 550 ℃ of air, roasting is 5 hours, obtains the Pt-Ag-Th catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.5wt%, and Ag quality percentage composition is 0.2wt%, and Th quality percentage composition is 0.15wt%, and diatomite quality percentage composition is 99.15wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 2.5 ℃/min under atmosphere is elevated to 500 ℃, and at this temperature, reduction is 3 hours, H
2gas space velocity GHSV=7500 h
-1.280 ℃ of reaction temperatures, reaction pressure is at 2 MPa, acetic acid liquid air speed LHSV=2 h
-1, H
2: the acetic acid mol ratio is 20.Under reaction condition as mentioned above, acetic acid conversion ratio 96.6%, ethanol selective 96.2%.
Embodiment 13:
15 g APTES are joined in 100 ml ethanol, be mixed with solution.12 g silica are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 24 hours.Mixture after backflow is with after ethanol washing, 65 ℃ of dryings 3 hours, obtains the silica after the APTES modification.Platinum acid chloride solution 20 ml that compound concentration is 0.0145 mol/L, on the silica by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 5 hours, then under 120 ℃ dry 8 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 30 ml 0.35 M, stir reduction 55 min, filter afterwards, wash away chlorion, at room temperature place 3 hours, then under 120 ℃ dry 6 hours, obtain the silica after supporting Pt.Liquor argenti nitratis ophthalmicus 20 ml that compound concentration is 0.1139 mol/L, on the silica by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 4 hours, then under 120 ℃ dry 8 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 20 ml 0.25 M, stirred reduction 55 min, wash afterwards, filter, at room temperature place 2 hours, under 100 ℃, drying is 6 hours, obtains the catalyst without metal promoter.Ammonium metatungstate mixed solution 20 ml that the nickel nitrate that compound concentration is 0.0021 mol/L and concentration are 0.0012 mol/L, by above-mentioned solution incipient impregnation on the catalyst without metal promoter, at room temperature place 2 hours, under 110 ℃, drying is 10 hours, in 600 ℃ of air, roasting is 4 hours, obtains the Pt-Ag-Ni catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.46wt%, and Ag quality percentage composition is 2wt%, and Ni quality percentage composition is 0.02wt%, and W quality percentage composition is 0.25wt%, and silica quality percentage composition is 97.27wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 1.5 ℃/min under atmosphere is elevated to 600 ℃, and at this temperature, reduction is 8 hours, H
2gas space velocity GHSV=7500 h
-1.280 ℃ of reaction temperatures, reaction pressure is at 3MPa, acetic acid liquid air speed LHSV=1.5 h
-1, H
2: the acetic acid mol ratio is 25.Under reaction condition as mentioned above, acetic acid conversion ratio 92.5%, ethanol selective 95.8%.
Embodiment 14:
14 g APTES are joined in 140 ml ethanol, be mixed with solution.10 g titanium dioxide are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 24 hours.Mixture after backflow is with after ethanol washing, 60 ℃ of dryings 3 hours, obtains the titanium dioxide after the APTES modification.Platinum acid chloride solution 10 ml that compound concentration is 0.0237 mol/L, on the titanium dioxide by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 5 hours, then under 110 ℃ dry 10 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 40 ml 0.2 M, stir reductase 12 5 min, filter afterwards, wash away chlorion, at room temperature place 5 hours, then under 100 ℃ dry 10 hours, obtain the titanium dioxide after supporting Pt.Liquor argenti nitratis ophthalmicus 10 ml that compound concentration is 0.1710 mol/L, on the titanium dioxide by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 2 hours, then under 120 ℃ dry 8 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 25 ml 0.25 M, stirred reductase 12 0 min, wash afterwards, filter, at room temperature place 4 hours, under 120 ℃, drying is 7 hours, obtains the catalyst without metal promoter.Cobalt nitrate solution 10 ml that compound concentration is 0.0487 mol/L, the cobalt nitrate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 3 hours, and under 100 ℃, drying is 12 hours, in 400 ℃ of air, roasting is 5 hours, obtains the Pt-Ag-Co catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.45wt%, and Ag quality percentage composition is 1.8wt%, and Co quality percentage composition is 0.28wt%, and titanium dioxide quality percentage composition is 97.47wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 1.5 ℃/min under atmosphere is elevated to 400 ℃, and at this temperature, reduction is 4 hours, H
2gas space velocity GHSV=7500 h
-1.230 ℃ of reaction temperatures, reaction pressure is at 1MPa, acetic acid liquid air speed LHSV=1 h
-1, H
2: the acetic acid mol ratio is 50.Under reaction condition as mentioned above, acetic acid conversion ratio 100%, ethanol selective 92.0%.
Embodiment 15:
10 g APTES are joined in 150 ml ethanol, be mixed with solution.16 g zirconias are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 18 hours.Mixture after backflow is with after ethanol washing, 65 ℃ of dryings 4 hours, obtains the zirconia after the APTES modification.Platinum acid chloride solution 25 ml that compound concentration is 0.0086 mol/L, on the zirconia by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 3 hours, then under 110 ℃ dry 9 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 25 ml 0.3 M, stir reduction 60 min, filter afterwards, wash away chlorion, at room temperature place 2 hours, then under 120 ℃ dry 9 hours, obtain the zirconia after supporting Pt.Liquor argenti nitratis ophthalmicus 25 ml that compound concentration is 0.0180 mol/L, on the zirconia by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 5 hours, then under 110 ℃ dry 12 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 30 ml 0.3 M, stirred reduction 50 min, wash afterwards, filter, at room temperature place 5 hours, under 110 ℃, drying is 10 hours, obtains the catalyst without metal promoter.Ammonium molybdate solution 25 ml that compound concentration is 0.0048 mol/L, the ammonium molybdate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 5 hours, and under 120 ℃, drying is 10 hours, in 550 ℃ of air, roasting is 4 hours, obtains the Pt-Ag-Mo catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.26wt%, and Ag quality percentage composition is 0.3wt%, and Mo quality percentage composition is 0.5wt%, and zirconia quality percentage composition is 98.94wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 0.5 ℃/min under atmosphere is elevated to 450 ℃, and at this temperature, reduction is 8 hours, H
2gas space velocity GHSV=6000 h
-1.220 ℃ of reaction temperatures, reaction pressure is at 2MPa, acetic acid liquid air speed LHSV=2.5 h
-1, H
2: the acetic acid mol ratio is 40.Under reaction condition as mentioned above, acetic acid conversion ratio 95.3%, ethanol selective 91.2%.
Embodiment 16:
13 g APTES are joined in 120 ml ethanol, be mixed with solution.20 g diatomite are joined in above-mentioned APTES ethanolic solution, mixture is refluxed 22 hours.Mixture after backflow is with after ethanol washing, 60 ℃ of dryings 2 hours, obtains the diatomite after the APTES modification.Platinum acid chloride solution 30 ml that compound concentration is 0.0103 mol/L, on the diatomite by the platinum acid chloride solution incipient impregnation after the APTES modification.Carrier after the load chloroplatinic acid is at room temperature placed 2 hours, then under 120 ℃ dry 6 hours, obtain sample 1.Sample 1 is joined to the solution of potassium borohydride of 35 ml 0.25 M, stir reduction 50 min, filter afterwards, wash away chlorion, at room temperature place 3 hours, then under 110 ℃ dry 8 hours, obtain the diatomite after supporting Pt.Liquor argenti nitratis ophthalmicus 30 ml that compound concentration is 0.0124 mol/L, on the diatomite by the liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature place 2 hours, then under 100 ℃ dry 8 hours, obtain sample 2.Sample 2 is put into to the solution of potassium borohydride of 30 ml 0.3 M, stirred reduction 30 min, wash afterwards, filter, at room temperature place 3 hours, under 110 ℃, drying is 12 hours, obtains the catalyst without metal promoter.Ammonium metatungstate solution 30 ml that compound concentration is 0.0008 mol/L, the ammonium metatungstate solution incipient impregnation, on the catalyst without metal promoter, is at room temperature placed 2 hours, and under 110 ℃, drying is 7 hours, in 600 ℃ of air, roasting is 3 hours, obtains the Pt-Ag-W catalyst.Above-mentioned catalyst Pt quality percentage composition is 0.3wt%, and Ag quality percentage composition is 0.2wt%, and W quality percentage composition is 0.25wt%, and diatomite quality percentage composition is 99.25wt%.
Above-mentioned catalyst 2 ml are filled in fixed-bed tube reactor.Concrete application conditions is as follows: by catalyst at H
2heating rate with 2.5 ℃/min under atmosphere is elevated to 550 ℃, and at this temperature, reduction is 6 hours, H
2gas space velocity GHSV=6000 h
-1.290 ℃ of reaction temperatures, reaction pressure is at 2.5 MPa, acetic acid liquid air speed LHSV=1.5 h
-1, H
2: the acetic acid mol ratio is 30.Under reaction condition as mentioned above, acetic acid conversion ratio 94.7%, ethanol selective 93.9%.
Claims (4)
1. the catalyst of an acetic acid hydrogenation synthesizing alcohol is characterized in that catalyst consists of:
Pt load capacity 0.3-0.5wt%, Ag load capacity 0.02-2.8wt%, the load capacity of metal promoter is 0-0.5wt%, surplus is carrier;
And preparation by the following method:
(1) the 3-aminopropyl triethoxysilane is joined in ethanolic solution and be made into 3-aminopropyl triethoxysilane ethanolic solution, again carrier is joined in 3-aminopropyl triethoxysilane ethanolic solution, 3-aminopropyl triethoxysilane wherein: ethanol: carrier=10-15 g:100-150 ml:10-20 g, by the mixture 18-30 hour that refluxes, mixture after backflow is with after the ethanol washing, at 60-80 ℃ of dry 2-5 hour, obtain the carrier after the modification of 3-aminopropyl triethoxysilane;
(2) platinum acid chloride solution that compound concentration is 0.0086-0.0382 mol/L, on carrier by the platinum acid chloride solution incipient impregnation after the modification of step (1) 3-aminopropyl triethoxysilane, wherein, carrier after the modification of 3-aminopropyl triethoxysilane: platinum acid chloride solution=10-20 g:10-30 ml, carrier after the load chloroplatinic acid is at room temperature placed 2-5 hour, obtain sample 1 after dry 6-12 hour again under 100-120 ℃, sample 1 is joined in the solution of potassium borohydride of 0.2-0.4 M and stir reductase 12 0-60 min, wherein, sample 1: solution of potassium borohydride=10-20 g:20-40 ml, afterwards sample 1 is at room temperature placed to 2-5 hour, dry 6-12 hour under 100-120 ℃ again, obtain supporting Pt carrier afterwards,
(3) liquor argenti nitratis ophthalmicus of preparation 0.0007-0.4830 mol/L, on carrier by the liquor argenti nitratis ophthalmicus incipient impregnation after step (2) supporting Pt, wherein, carrier after supporting Pt: liquor argenti nitratis ophthalmicus=10-20 g:10-30 ml, carrier after the load silver nitrate is at room temperature placed 2-5 hour, obtain sample 2 after dry 6-12 hour again under 100-120 ℃, sample 2 is joined in the solution of potassium borohydride of 0.2-0.4 M and stir reductase 12 0-60 min, wherein, sample 2: solution of potassium borohydride=5-10 g:20-40 ml, afterwards sample is at room temperature placed to 2-5 hour, dry 6-12 hour under 100-120 ℃ again, obtain the catalyst without metal promoter,
(4) for the metal promoter load capacity > preparation of the catalyst of 0wt%, solubility is joined in deionized water containing auxiliary compound, be mixed with the metal promoter solution of 0.0008-0.0811 mol/L, by metal promoter solution incipient impregnation in step (3) catalyst without metal promoter, wherein, catalyst without metal promoter: metal promoter solution=10-20 g:10-30 ml, the catalyst of carried metal auxiliary compound is at room temperature placed to 2-5 hour, dry 6-12 hour under 100-120 ℃ again, roasting 3-6 hour in 400-600 ℃ of air, obtain the catalyst of containing metal auxiliary agent.
2. the catalyst of a kind of acetic acid hydrogenation synthesizing alcohol as claimed in claim 1, is characterized in that described metal promoter is one or more of Mo, Sn, Co, W, Cr, Mn, Fe, Ni, Cu, Zn, Ru, Rh, Pd, La, Ce, Th.
3. the catalyst of a kind of acetic acid hydrogenation synthesizing alcohol as claimed in claim 1, is characterized in that described carrier is alundum (Al2O3), molecular sieve, silica, titanium dioxide, zirconia or diatomite.
4. the application of the catalyst of a kind of acetic acid hydrogenation synthesizing alcohol as described as claim 1-3 any one, is characterized in that catalyst is applied in fixed-bed tube reactor, and reducing condition is: by catalyst at H
2under atmosphere, with the heating rate of 0.5-3 ℃/min, be elevated to 400-600 ℃ of reduction 3-8 hour, H
2gas space velocity GHSV=1500-9000 h
-1; Reaction condition is: in reaction temperature 200-300 ℃ of scope, reaction pressure is at 1.0-3.0 MPa, acetic acid liquid air speed LHSV=0.5-3 h
-1, H
2: the acetic acid mol ratio is 5-50.
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| CN102847544B (en) * | 2012-09-26 | 2015-05-13 | 厦门大学 | Catalytic agent for preparing ethanol by using acetic acid hydrogenation and preparation method thereof |
| CN103787829B (en) * | 2012-10-31 | 2015-10-07 | 中国石油化工股份有限公司 | A kind of cobalt silver catalyst hydrogenation of carboxylic acids prepares the method for alcohol |
| CN104043484B (en) * | 2013-03-13 | 2016-10-12 | 中国石油天然气股份有限公司 | A kind of acetic acid catalytic hydrogenation prepares the catalyst of ethanol and preparation thereof and application |
| CN103691450B (en) * | 2014-01-06 | 2015-11-11 | 神华集团有限责任公司 | A kind of Catalysts and its preparation method of acetic acid hydrogenation ethanol |
| CN105709777B (en) * | 2014-12-03 | 2019-05-31 | 神华集团有限责任公司 | The method of catalyst of acetic acid hydrogenation ethyl alcohol and preparation method thereof and acetic acid hydrogenation ethyl alcohol |
| CN108607600B (en) * | 2016-12-10 | 2020-09-08 | 中国科学院大连化学物理研究所 | Catalyst with high-dispersion noble metal loaded on molecular sieve, and preparation and application thereof |
| CN106732771B (en) * | 2016-12-16 | 2019-02-05 | 洛阳师范学院 | A kind of preparation method of hydrophobic nano silicon ball load palladium-based catalyst |
| CN108940273B (en) * | 2017-05-18 | 2021-06-04 | 湖南长岭石化科技开发有限公司 | Hydrogenation catalyst, preparation method and application thereof, and hydrogenation reaction method |
| CN109420492B (en) * | 2017-08-22 | 2022-04-12 | 湖南长岭石化科技开发有限公司 | Hydrogenation catalyst, preparation method and application thereof, and phenol hydrogenation reaction method |
| CN108435174B (en) * | 2018-04-27 | 2020-02-18 | 中国科学院山西煤炭化学研究所 | Catalyst for treating high-concentration organic wastewater and preparation method and application thereof |
| CN112371173B (en) * | 2020-11-27 | 2023-09-08 | 沈阳化工研究院有限公司 | Platinum-carbon catalyst applied to hydrogenation of m-nitrobenzenesulfonic acid and preparation method thereof |
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