CN102614914A - 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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- CN102614914A CN102614914A CN2012100575688A CN201210057568A CN102614914A CN 102614914 A CN102614914 A CN 102614914A CN 2012100575688 A CN2012100575688 A CN 2012100575688A CN 201210057568 A CN201210057568 A CN 201210057568A CN 102614914 A CN102614914 A CN 102614914A
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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 oxygenation agent 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 discharging.The industrial process of alcohol fuel is mainly grain and industrial crops fermentation method at present.China's raw material for fuel ethanol production is mainly corn and wheat, not only cost height but also serious threat national food safety.
Non-grain route method ethanol production receives increasing attention, and patent CN101235392, CN101289677 have reported to be the alcohol production technology of raw material with the cellulose.Cellulose fermentation is produced the ethanol technology and has been overcome the problem that the grain fermentation method occupies cultivated land, but owing to factors such as the cellulase cost is high, the cellulose energy density is low cause the cellulosic ethanol production cost high, makes this technological industrialization development be restricted.Patent CN1225852 has reported that this process receives the ASF distribution limitation from the technology of one step of synthesis gas synthesizing alcohol, and the ethanol selectivity is 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 the 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 load capacity 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 support type Pt catalyst in the acetic acid hydrogenation, demonstrate catalytic performance preferably, Pt load capacity still higher (0.5-1.0wt%) still.
Summary of the invention
The objective of the invention is to present acetic acid hydrogenation catalyst noble metal load capacity highly, cost is high, and the shortcoming of poor selectivity provides a kind of catalyst and preparation method and application of high, acetic acid hydrogenation synthesizing alcohol that the ethanol selectivity is high 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 a carrier.
Aforesaid metal promoter is one or more of Mo, Sn, Co, W, Cr, Mn, Fe, Ni, Cu, Zn, Ru, Rh, Pd, La, Ce, Th.
Aforesaid carrier is alundum (Al, 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 basically at present, and the dispersion of Pt on carrier is difficult to control.This mainly shows two aspects: one, the defective bit of carrier surface absorption Pt is limited, and Pt is difficult to high degree of dispersion on carrier when causing flooding; Two, the catalyst precursor of supporting Pt compound is prone to take place metal agglomeration 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 the organo-functional group modification, make its surface form the adsorption potential of absorption Pt compound.Secondly, the Pt that loads on the carrier is carried out Alloying Treatment, reduce its sintering degree in roasting process.
Preparation of catalysts method provided by the invention may further comprise the steps:
(1) APTES (3-aminopropyl triethoxysilane) is joined is made into the APTES ethanolic solution in the ethanolic solution; Again carrier is joined in the APTES ethanolic solution; APTES wherein: ethanol: carrier=10-15 g:100-150 ml:10-20 g, mixture was refluxed 18-30 hour, the mixture after the backflow with washing with alcohol after; At 60-80 ℃ of dry 2-5 hour, obtain the carrier after the APTES modification;
(2) compound concentration is the platinum acid chloride solution of 0.0086-0.0382 mol/L; With the platinum acid chloride solution incipient impregnation on the carrier after step (1) the APTES modification, wherein, the carrier after the APTES modification: platinum acid chloride solution=10-20 g:10-30 ml; Carrier behind the load chloroplatinic acid was at room temperature placed 2-5 hour; Down obtain sample 1 after dry 6-12 hour at 100-120 ℃ again, 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 was at room temperature placed 2-5 hour, descended dry 6-12 hour at 100-120 ℃ again, obtain supporting Pt carrier afterwards;
(3) liquor argenti nitratis ophthalmicus of preparation 0.0007-0.4830 mol/L, with the liquor argenti nitratis ophthalmicus incipient impregnation on the carrier after step (2) supporting Pt, wherein; Carrier after the supporting Pt: liquor argenti nitratis ophthalmicus=10-20 g:10-30 ml, the carrier behind the load silver nitrate was at room temperature placed 2-5 hour, after under 100-120 ℃ dry 6-12 hour, obtained sample 2 again; Sample 2 is joined stir reductase 12 0-60 min in the solution of potassium borohydride of 0.2-0.4 M; Wherein, sample 2: solution of potassium borohydride=5-10 g:20-40 ml, afterwards sample was at room temperature placed 2-5 hour; Descended dry 6-12 hour at 100-120 ℃ again, obtain not having the catalyst of metal promoter;
(4) for the metal promoter load capacity>Preparation of catalysts of 0wt%; Solubility is contained auxiliary compound join in the deionized water, be mixed with the metal promoter solution of 0.0008-0.0811 mol/L, with the catalyst of metal promoter solution incipient impregnation in the no metal promoter of step (3); Wherein, The catalyst of no metal promoter: metal promoter solution=10-20 g:10-30 ml, the catalyst of carried metal auxiliary compound was at room temperature placed 2-5 hour, descended dry 6-12 hour at 100-120 ℃ again; In the 400-600 ℃ of air roasting 3-6 hour, obtain the catalyst of containing metal auxiliary agent.
Aforesaid all kinds of Pt-Ag catalyst can be applicable in the fixed-bed tube reactor.Concrete reducing condition is following: with catalyst at H
2Under the atmosphere, be elevated to 400-600 ℃ of reduction 3-8 hour, H with the heating rate of 0.5-3 ℃/min
2Gas space velocity GHSV=1500-9000 h
-1Reaction condition is: in the 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 stated, the acetic acid conversion ratio is greater than 90%, and the ethanol selectivity is greater than 85%.
The present invention's advantage compared with prior art:
1, support type Pt-Ag catalyst provided by the invention uses APTES to form the metal of alloy as the modifier of carrier surface functionalization, Ag conduct and Pt.
2, method for preparing catalyst noble metal load capacity provided by the invention is low, and production cost is low.
3, catalyst applications of the present invention is gentle in acetic acid hydrogenation synthesizing alcohol reaction condition, and the acetic acid conversion ratio is high, the ethanol selectivity is 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
Provide several illustrative rather than restrictive example below:
Embodiment 1:
15 g APTES are joined in the 100 ml ethanol, be mixed with solution.12 g silica are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 18 hours.Mixture after the backflow with washing with alcohol after, 75 ℃ of dryings 4 hours, obtain the silica after the APTES modification.Compound concentration is platinum acid chloride solution 20 ml of 0.0131 mol/L, with the platinum acid chloride solution incipient impregnation on the silica after the APTES modification.Silica behind the load chloroplatinic acid was at room temperature placed 2 hours, descended dry 11 hours at 120 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 30 ml, 0.4 M, stirs reductase 12 0 min, filter, wash away chlorion afterwards, at room temperature placed 3 hours, again 110 ℃ dry 6 hours down, obtain the silica after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 20 ml of 0.0564 mol/L, and the liquor argenti nitratis ophthalmicus incipient impregnation on the silica after the supporting Pt, was at room temperature placed 3 hours, descends dry 8 hours at 100 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 20 ml, 0.25 M, stirs reduction 35 min, wash afterwards, filter, at room temperature placed 5 hours, 110 ℃ dry 11 hours down, obtain not having the catalyst of 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 the fixed-bed tube reactor.Concrete application conditions is following: catalyst is at H
2Heating rate with 2 ℃/min under the atmosphere is elevated to 450 ℃ of reduction 3 hours, H
2Gas space velocity GHSV=4500 h
-1200 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 96.5%, ethanol selectivity 86.5%.
Embodiment 2:
15 g APTES are joined in the 100 ml ethanol, be mixed with solution.12 g silica are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 26 hours.Mixture after the backflow with washing with alcohol after, 70 ℃ of dryings 5 hours, obtain the silica after the APTES modification.Compound concentration is platinum acid chloride solution 20 ml of 0.0100 mol/L, with the platinum acid chloride solution incipient impregnation on the silica after the APTES modification.Silica behind the load chloroplatinic acid was at room temperature placed 4 hours, descended dry 12 hours at 110 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 30 ml, 0.3 M, stirs reduction 40 min, filter, wash away chlorion afterwards, at room temperature placed 2 hours, again 100 ℃ dry 9 hours down, obtain the silica after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 20 ml of 0.0281 mol/L, on the silica of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 2 hours, descends dry 12 hours at 120 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 20 ml, 0.35 M, stirs reduction 45 min, wash afterwards, filter, at room temperature placed 3 hours, 110 ℃ dry 10 hours down, obtain not having the catalyst of metal promoter.Compound concentration is manganese nitrate solution 20 ml of 0.0276 mol/L; The manganese nitrate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 3 hours, and drying is 10 hours under 120 ℃; Roasting is 4 hours in 400 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: catalyst is at H
2Heating rate with 0.5 ℃/min under the atmosphere is elevated to 400 ℃ of reduction 7 hours, H
2Gas space velocity GHSV=1500 h
-1250 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 98.3%, ethanol selectivity 95.5%.
Embodiment 3:
12 g APTES are joined in the 130 ml ethanol, be mixed with solution.18 g alundum (Als are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 24 hours.Mixture after the backflow with washing with alcohol after, 70 ℃ of dryings 3 hours, obtain the alundum (Al after the APTES modification.Compound concentration is platinum acid chloride solution 10 ml of 0.0354 mol/L, with the platinum acid chloride solution incipient impregnation on the alundum (Al after the APTES modification.Alundum (Al behind the load chloroplatinic acid was at room temperature placed 3 hours, descended dry 8 hours at 100 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 20 ml, 0.35 M, stirs reduction 55 min, filter, wash away chlorion afterwards, at room temperature placed 4 hours, again 120 ℃ dry 8 hours down, obtain the alundum (Al after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 10 ml of 0.0084 mol/L, on the alundum (Al of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 5 hours, descends dry 11 hours at 110 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 25 ml, 0.3 M, stirs reduction 40 min, wash afterwards, filter, at room temperature placed 2 hours, 100 ℃ dry 8 hours down, obtain not having the catalyst of metal promoter.Compound concentration is iron nitrate solution 10 ml of 0.1622 mol/L; The iron nitrate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 2 hours, and drying is 8 hours under 110 ℃; Roasting is 6 hours in 550 ℃ of air, 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 (Al quality percentage composition is 99.07wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 1 ℃/min under the atmosphere is elevated to 550 ℃, and reduction is 6 hours under this temperature, H
2Gas space velocity GHSV=6000 h
-1230 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 90.5%, ethanol selectivity 92.4%.
Embodiment 4:
10 g APTES are joined in the 150 ml ethanol, be mixed with solution.10 g titanium dioxide are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 24 hours.Mixture after the backflow with washing with alcohol after, 65 ℃ of dryings 4 hours, obtain the titanium dioxide after the APTES modification.Compound concentration is platinum acid chloride solution 10 ml of 0.0258 mol/L, with the platinum acid chloride solution incipient impregnation on the titanium dioxide after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 5 hours, descended dry 7 hours at 110 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 25 ml, 0.35 M, stirs reduction 60 min, filter, wash away chlorion afterwards, at room temperature placed 5 hours, again 110 ℃ dry 7 hours down, obtain the titanium dioxide after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 10 ml of 0.0019 mol/L, on the titanium dioxide of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 2 hours, descends dry 7 hours at 100 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 40 ml, 0.2 M, stirs reductase 12 0 min, wash afterwards, filter, at room temperature placed 3 hours, 120 ℃ dry 9 hours down, obtain not having the catalyst of metal promoter.Compound concentration is stannous chloride solution 10 ml of 0.0085 mol/L; Stannous chloride solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 2 hours, and drying is 11 hours under 110 ℃; Roasting is 6 hours in 600 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 1 ℃/min under the atmosphere is elevated to 600 ℃, and reduction is 4 hours under this temperature, H
2Gas space velocity GHSV=6000 h
-1240 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 100%, ethanol selectivity 90.5%.
Embodiment 5:
10 g APTES are joined in the 150 ml ethanol, be mixed with solution.16 g zirconias are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 18 hours.Mixture after the backflow with washing with alcohol after, 65 ℃ of dryings 3 hours, obtain the zirconia after the APTES modification.Compound concentration is platinum acid chloride solution 25 ml of 0.0113 mol/L, with the platinum acid chloride solution incipient impregnation on the zirconia after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 2 hours, descended dry 6 hours at 120 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 25 ml, 0.25 M, stirs reductase 12 5 min, filter, wash away chlorion afterwards, at room temperature placed 3 hours, again 120 ℃ dry 11 hours down, obtain the zirconia after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 25 ml of 0.0060 mol/L, on the zirconia of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 5 hours, descends dry 8 hours at 110 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 40 ml, 0.25 M, stirs reduction 50 min, wash afterwards, filter, at room temperature placed 5 hours, 120 ℃ dry 7 hours down, obtain not having the catalyst of metal promoter.Compound concentration is chromium nitrate solution 25 ml of 0.0621 mol/L; The chromium nitrate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 5 hours, and drying is 7 hours under 100 ℃; Roasting is 5 hours in 400 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 3 ℃/min under the atmosphere is elevated to 600 ℃, and reduction is 5 hours under this temperature, H
2Gas space velocity GHSV=7500 h
-1280 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 90.5%, ethanol selectivity 96.3%.
Embodiment 6:
13 g APTES are joined in the 120 ml ethanol, be mixed with solution.20 g diatomite are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 22 hours.Mixture after the backflow with washing with alcohol after, 60 ℃ of dryings 2 hours, obtain the diatomite after the APTES modification.Compound concentration is platinum acid chloride solution 30 ml of 0.0155 mol/L, with the platinum acid chloride solution incipient impregnation on the diatomite after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 5 hours, descended dry 7 hours at 100 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 35 ml, 0.2 M, stirs reduction 60 min, filter, wash away chlorion afterwards, at room temperature placed 2 hours, again 120 ℃ dry 12 hours down, obtain the diatomite after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 30 ml of 0.1530 mol/L, on the diatomite of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 3 hours, descends dry 9 hours at 120 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 30 ml, 0.3 M, stirs reductase 12 5 min, wash afterwards, filter, at room temperature placed 2 hours, 100 ℃ dry 8 hours down, obtain not having the catalyst of metal promoter.Compound concentration is zinc nitrate solution 30 ml of 0.0371 mol/L; The zinc nitrate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 2 hours, and drying is 12 hours under 120 ℃; Roasting is 4 hours in 400 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 1.5 ℃/min under the atmosphere is elevated to 400 ℃, and reduction is 5 hours under this temperature, H
2Gas space velocity GHSV=3000 h
-1260 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 90.7%, ethanol selectivity 85.2%.
Embodiment 7:
15 g APTES are joined in the 100 ml ethanol, be mixed with solution.12 g silica are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 22 hours.Mixture after the backflow with washing with alcohol after, 65 ℃ of dryings 5 hours, obtain the silica after the APTES modification.Compound concentration is platinum acid chloride solution 20 ml of 0.0151 mol/L, with the platinum acid chloride solution incipient impregnation on the silica after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 3 hours, descended dry 6 hours at 110 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 30 ml, 0.3 M, stirs reduction 55 min, filter, wash away chlorion afterwards, at room temperature placed 5 hours, again 100 ℃ dry 6 hours down, obtain the silica after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 20 ml of 0.0854 mol/L, on the silica of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 4 hours, descends dry 6 hours at 100 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 20 ml, 0.2 M, stirs reduction 45 min, wash afterwards, filter, at room temperature placed 4 hours, 110 ℃ dry 12 hours down, obtain not having the catalyst of metal promoter.Compound concentration is ruthenium trichloride solution 20 ml of 0.0243 mol/L; Ruthenium trichloride solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 4 hours, and drying is 10 hours under 120 ℃; Roasting is 3 hours in 600 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 0.5 ℃/min under the atmosphere is elevated to 400 ℃, and reduction is 6 hours under this temperature, H
2Gas space velocity GHSV=1500 h
-1240 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 92.1%, ethanol selectivity 94.8%.
Embodiment 8:
15 g APTES are joined in the 100 ml ethanol, be mixed with solution.12 g silica are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 28 hours.Mixture after the backflow with washing with alcohol after, 60 ℃ of dryings 2 hours, obtain the silica after the APTES modification.Compound concentration is platinum acid chloride solution 20 ml of 0.0093 mol/L, with the platinum acid chloride solution incipient impregnation on the silica after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 2 hours, descended dry 10 hours at 110 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 30 ml, 0.25 M, stirs reduction 30 min, filter, wash away chlorion afterwards, at room temperature placed 2 hours, again 110 ℃ dry 9 hours down, obtain the silica after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 20 ml of 0.0045 mol/L, on the silica of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 3 hours, descends dry 10 hours at 110 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 20 ml, 0.25 M, stirs reduction 50 min, wash afterwards, filter, at room temperature placed 2 hours, 110 ℃ dry 6 hours down, obtain not having the catalyst of metal promoter.Preparation rhodium chloride concentration is that 0.0029 mol/L and lanthanum nitrate concentration are mixed solution 20 ml of 0.0146 mol/L; With above-mentioned solution incipient impregnation on the catalyst of no metal promoter; At room temperature placed 4 hours; Drying is 6 hours under 110 ℃, and roasting is 6 hours in 450 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 1.5 ℃/min under the atmosphere is elevated to 450 ℃, and reduction is 8 hours under this temperature, H
2Gas space velocity GHSV=9000 h
-1210 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 96.4%, ethanol selectivity 87.8%.
Embodiment 9:
12 g APTES are joined in the 130 ml ethanol, be mixed with solution.18 g alundum (Als are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 30 hours.Mixture after the backflow with washing with alcohol after, 75 ℃ of dryings 5 hours, obtain the alundum (Al after the APTES modification.Compound concentration is platinum acid chloride solution 10 ml of 0.0382 mol/L, with the platinum acid chloride solution incipient impregnation on the alundum (Al after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 3 hours, descended dry 9 hours at 100 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 20 ml, 0.2 M, stirs reduction 50 min, filter, wash away chlorion afterwards, at room temperature placed 3 hours, again 110 ℃ dry 10 hours down, obtain the alundum (Al after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 10 ml of 0.4830 mol/L, on the alundum (Al of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 2 hours, descends dry 7 hours at 120 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 25 ml, 0.35 M, stirs reduction 30 min, wash afterwards, filter, at room temperature placed 3 hours, 120 ℃ dry 7 hours down, obtain not having the catalyst of metal promoter.Compound concentration is palladium chloride solution 10 ml of 0.0316 mol/L; The palladium chloride solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 5 hours, and drying is 8 hours under 100 ℃; Roasting is 4 hours in 500 ℃ of air, 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 (Al quality percentage composition is 96.62wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 2.5 ℃/min under the atmosphere is elevated to 550 ℃, and reduction is 4 hours under this temperature, H
2Gas space velocity GHSV=3000 h
-1260 ℃ of reaction temperatures, reaction pressure be at 2MPa, acetic acid liquid air speed LHSV=3 h
-1, H
2: the acetic acid mol ratio is 40.Under reaction condition as stated, acetic acid conversion ratio 92.3%, ethanol selectivity 89.7%.
Embodiment 10:
14 g APTES are joined in the 140 ml ethanol, be mixed with solution.10 g titanium dioxide are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 28 hours.Mixture after the backflow with washing with alcohol after, 80 ℃ of dryings 5 hours, obtain the titanium dioxide after the APTES modification.Compound concentration is platinum acid chloride solution 10 ml of 0.0239 mol/L, with the platinum acid chloride solution incipient impregnation on the titanium dioxide after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 4 hours, descended dry 8 hours at 100 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 40 ml, 0.3 M, stirs reduction 45 min, filter, wash away chlorion afterwards, at room temperature placed 5 hours, again 100 ℃ dry 10 hours down, obtain the titanium dioxide after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 10 ml of 0.0468 mol/L, on the titanium dioxide of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 5 hours, descends dry 6 hours at 100 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 25 ml, 0.35 M, stirs reduction 45 min, wash afterwards, filter, at room temperature placed 3 hours, 100 ℃ dry 9 hours down, obtain not having the catalyst of metal promoter.Compound concentration is lanthanum nitrate hexahydrate 10 ml of 0.0146 mol/L; The lanthanum nitrate hexahydrate incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 3 hours, and drying is 9 hours under 120 ℃; Roasting is 3 hours in 500 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 3 ℃/min under the atmosphere is elevated to 500 ℃, and reduction is 7 hours under this temperature, H
2Gas space velocity GHSV=9000 h
-1270 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 100%, ethanol selectivity 93.5%.
Embodiment 11:
10 g APTES are joined in the 150 ml ethanol, be mixed with solution.16 g zirconias are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 26 hours.Mixture after the backflow with washing with alcohol after, 75 ℃ of dryings 2 hours, obtain the zirconia after the APTES modification.Compound concentration is platinum acid chloride solution 25 ml of 0.0118 mol/L, with the platinum acid chloride solution incipient impregnation on the zirconia after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 4 hours, descended dry 10 hours at 110 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 25 ml, 0.35 M, stirs reduction 35 min, filter, wash away chlorion afterwards, at room temperature placed 4 hours, again 100 ℃ dry 8 hours down, obtain the zirconia after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 25 ml of 0.1219 mol/L, on the zirconia of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 3 hours, descends dry 8 hours at 120 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 40 ml, 0.3 M, stirs reduction 35 min, wash afterwards, filter, at room temperature placed 2 hours, 110 ℃ dry 9 hours down, obtain not having the catalyst of metal promoter.Compound concentration is cerous nitrate solution 25 ml of 0.0212 mol/L; The cerous nitrate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 2 hours, and drying is 7 hours under 110 ℃; Roasting is 5 hours in 450 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 2 ℃/min under the atmosphere is elevated to 450 ℃, and reduction is 8 hours under this temperature, H
2Gas space velocity GHSV=4500 h
-1220 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 92.5%, ethanol selectivity 88.4%.
Embodiment 12:
13 g APTES are joined in the 120 ml ethanol, be mixed with solution.20 g diatomite are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 20 hours.Mixture after the backflow with washing with alcohol after, 70 ℃ of dryings 4 hours, obtain the diatomite after the APTES modification.Compound concentration is platinum acid chloride solution 30 ml of 0.0172 mol/L, with the platinum acid chloride solution incipient impregnation on the diatomite after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 5 hours, descended dry 9 hours at 120 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 35 ml, 0.25 M, stirs reduction 40 min, filter, wash away chlorion afterwards, at room temperature placed 4 hours, again 100 ℃ dry 7 hours down, obtain the diatomite after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 30 ml of 0.0125 mol/L, on the diatomite of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 3 hours, descends dry 11 hours at 100 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 30 ml, 0.4 M, stirs reduction 40 min, wash afterwards, filter, at room temperature placed 5 hours, 120 ℃ dry 10 hours down, obtain not having the catalyst of metal promoter.Compound concentration is thorium nitrate solution 30 ml of 0.0043 mol/L; Thorium nitrate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 3 hours, and drying is 6 hours under 120 ℃; Roasting is 5 hours in 550 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 2.5 ℃/min under the atmosphere is elevated to 500 ℃, and reduction is 3 hours under this temperature, H
2Gas space velocity GHSV=7500 h
-1280 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 96.6%, ethanol selectivity 96.2%.
Embodiment 13:
15 g APTES are joined in the 100 ml ethanol, be mixed with solution.12 g silica are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 24 hours.Mixture after the backflow with washing with alcohol after, 65 ℃ of dryings 3 hours, obtain the silica after the APTES modification.Compound concentration is platinum acid chloride solution 20 ml of 0.0145 mol/L, with the platinum acid chloride solution incipient impregnation on the silica after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 5 hours, descended dry 8 hours at 120 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 30 ml, 0.35 M, stirs reduction 55 min, filter, wash away chlorion afterwards, at room temperature placed 3 hours, again 120 ℃ dry 6 hours down, obtain the silica after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 20 ml of 0.1139 mol/L, on the silica of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 4 hours, descends dry 8 hours at 120 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 20 ml, 0.25 M, stirs reduction 55 min, wash afterwards, filter, at room temperature placed 2 hours, 100 ℃ dry 6 hours down, obtain not having the catalyst of metal promoter.Compound concentration is the nickel nitrate of 0.0021 mol/L and ammonium metatungstate mixed solution 20 ml that concentration is 0.0012 mol/L; With above-mentioned solution incipient impregnation on the catalyst of no metal promoter; At room temperature placed 2 hours; Drying is 10 hours under 110 ℃, and roasting is 4 hours in 600 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 1.5 ℃/min under the atmosphere is elevated to 600 ℃, and reduction is 8 hours under this temperature, H
2Gas space velocity GHSV=7500 h
-1280 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 92.5%, ethanol selectivity 95.8%.
Embodiment 14:
14 g APTES are joined in the 140 ml ethanol, be mixed with solution.10 g titanium dioxide are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 24 hours.Mixture after the backflow with washing with alcohol after, 60 ℃ of dryings 3 hours, obtain the titanium dioxide after the APTES modification.Compound concentration is platinum acid chloride solution 10 ml of 0.0237 mol/L, with the platinum acid chloride solution incipient impregnation on the titanium dioxide after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 5 hours, descended dry 10 hours at 110 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 40 ml, 0.2 M, stirs reductase 12 5 min, filter, wash away chlorion afterwards, at room temperature placed 5 hours, again 100 ℃ dry 10 hours down, obtain the titanium dioxide after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 10 ml of 0.1710 mol/L, on the titanium dioxide of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 2 hours, descends dry 8 hours at 120 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 25 ml, 0.25 M, stirs reductase 12 0 min, wash afterwards, filter, at room temperature placed 4 hours, 120 ℃ dry 7 hours down, obtain not having the catalyst of metal promoter.Compound concentration is cobalt nitrate solution 10 ml of 0.0487 mol/L; The cobalt nitrate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 3 hours, and drying is 12 hours under 100 ℃; Roasting is 5 hours in 400 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 1.5 ℃/min under the atmosphere is elevated to 400 ℃, and reduction is 4 hours under this temperature, H
2Gas space velocity GHSV=7500 h
-1230 ℃ of reaction temperatures, reaction pressure be at 1MPa, acetic acid liquid air speed LHSV=1 h
-1, H
2: the acetic acid mol ratio is 50.Under reaction condition as stated, acetic acid conversion ratio 100%, ethanol selectivity 92.0%.
Embodiment 15:
10 g APTES are joined in the 150 ml ethanol, be mixed with solution.16 g zirconias are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 18 hours.Mixture after the backflow with washing with alcohol after, 65 ℃ of dryings 4 hours, obtain the zirconia after the APTES modification.Compound concentration is platinum acid chloride solution 25 ml of 0.0086 mol/L, with the platinum acid chloride solution incipient impregnation on the zirconia after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 3 hours, descended dry 9 hours at 110 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 25 ml, 0.3 M, stirs reduction 60 min, filter, wash away chlorion afterwards, at room temperature placed 2 hours, again 120 ℃ dry 9 hours down, obtain the zirconia after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 25 ml of 0.0180 mol/L, on the zirconia of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 5 hours, descends dry 12 hours at 110 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 30 ml, 0.3 M, stirs reduction 50 min, wash afterwards, filter, at room temperature placed 5 hours, 110 ℃ dry 10 hours down, obtain not having the catalyst of metal promoter.Compound concentration is ammonium molybdate solution 25 ml of 0.0048 mol/L; The ammonium molybdate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 5 hours, and drying is 10 hours under 120 ℃; Roasting is 4 hours in 550 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 0.5 ℃/min under the atmosphere is elevated to 450 ℃, and reduction is 8 hours under this temperature, H
2Gas space velocity GHSV=6000 h
-1220 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 95.3%, ethanol selectivity 91.2%.
Embodiment 16:
13 g APTES are joined in the 120 ml ethanol, be mixed with solution.20 g diatomite are joined in the above-mentioned APTES ethanolic solution, mixture was refluxed 22 hours.Mixture after the backflow with washing with alcohol after, 60 ℃ of dryings 2 hours, obtain the diatomite after the APTES modification.Compound concentration is platinum acid chloride solution 30 ml of 0.0103 mol/L, with the platinum acid chloride solution incipient impregnation on the diatomite after the APTES modification.Carrier behind the load chloroplatinic acid was at room temperature placed 2 hours, descended dry 6 hours at 120 ℃ again, obtained sample 1.Sample 1 is joined the solution of potassium borohydride of 35 ml, 0.25 M, stirs reduction 50 min, filter, wash away chlorion afterwards, at room temperature placed 3 hours, again 110 ℃ dry 8 hours down, obtain the diatomite after the supporting Pt.Compound concentration is liquor argenti nitratis ophthalmicus 30 ml of 0.0124 mol/L, on the diatomite of liquor argenti nitratis ophthalmicus incipient impregnation after supporting Pt, at room temperature places 2 hours, descends dry 8 hours at 100 ℃ again, obtains sample 2.Sample 2 is put into the solution of potassium borohydride of 30 ml, 0.3 M, stirs reduction 30 min, wash afterwards, filter, at room temperature placed 3 hours, 110 ℃ dry 12 hours down, obtain not having the catalyst of metal promoter.Compound concentration is ammonium metatungstate solution 30 ml of 0.0008 mol/L; The ammonium metatungstate solution incipient impregnation on the catalyst of no metal promoter, was at room temperature placed 2 hours, and drying is 7 hours under 110 ℃; Roasting is 3 hours in 600 ℃ of air, 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 the fixed-bed tube reactor.Concrete application conditions is following: with catalyst at H
2Heating rate with 2.5 ℃/min under the atmosphere is elevated to 550 ℃, and reduction is 6 hours under this temperature, H
2Gas space velocity GHSV=6000 h
-1290 ℃ of reaction temperatures, reaction pressure be 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 stated, acetic acid conversion ratio 94.7%, ethanol selectivity 93.9%.
Claims (5)
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 a carrier.
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 (Al, molecular sieve, silica, titanium dioxide, zirconia or diatomite.
4. like the Preparation of catalysts method of each described a kind of acetic acid hydrogenation synthesizing alcohol of claim 1-3, it is characterized in that may further comprise the steps:
(1) the 3-aminopropyl triethoxysilane is joined is made into 3-aminopropyl triethoxysilane ethanolic solution in the ethanolic solution; Again carrier is joined in the 3-aminopropyl triethoxysilane ethanolic solution; 3-aminopropyl triethoxysilane wherein: ethanol: carrier=10-15 g:100-150 ml:10-20 g, mixture was refluxed 18-30 hour, the mixture after the backflow with washing with alcohol after; At 60-80 ℃ of dry 2-5 hour, obtain the carrier after the modification of 3-aminopropyl triethoxysilane;
(2) compound concentration is the platinum acid chloride solution of 0.0086-0.0382 mol/L; With the platinum acid chloride solution incipient impregnation on the carrier after the modification of step (1) 3-aminopropyl triethoxysilane, wherein, the carrier after the modification of 3-aminopropyl triethoxysilane: platinum acid chloride solution=10-20 g:10-30 ml; Carrier behind the load chloroplatinic acid was at room temperature placed 2-5 hour; Down obtain sample 1 after dry 6-12 hour at 100-120 ℃ again, 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 was at room temperature placed 2-5 hour, descended dry 6-12 hour at 100-120 ℃ again, obtain supporting Pt carrier afterwards;
(3) liquor argenti nitratis ophthalmicus of preparation 0.0007-0.4830 mol/L, with the liquor argenti nitratis ophthalmicus incipient impregnation on the carrier after step (2) supporting Pt, wherein; Carrier after the supporting Pt: liquor argenti nitratis ophthalmicus=10-20 g:10-30 ml, the carrier behind the load silver nitrate was at room temperature placed 2-5 hour, after under 100-120 ℃ dry 6-12 hour, obtained sample 2 again; Sample 2 is joined stir reductase 12 0-60 min in the solution of potassium borohydride of 0.2-0.4 M; Wherein, sample 2: solution of potassium borohydride=5-10 g:20-40 ml, afterwards sample was at room temperature placed 2-5 hour; Descended dry 6-12 hour at 100-120 ℃ again, obtain not having the catalyst of metal promoter;
(4) for the metal promoter load capacity>Preparation of catalysts of 0wt%; Solubility is contained auxiliary compound join in the deionized water, be mixed with the metal promoter solution of 0.0008-0.0811 mol/L, with the catalyst of metal promoter solution incipient impregnation in the no metal promoter of step (3); Wherein, The catalyst of no metal promoter: metal promoter solution=10-20 g:10-30 ml, the catalyst of carried metal auxiliary compound was at room temperature placed 2-5 hour, descended dry 6-12 hour at 100-120 ℃ again; In the 400-600 ℃ of air roasting 3-6 hour, obtain the catalyst of containing metal auxiliary agent.
5. like the Application of Catalyst of each described a kind of acetic acid hydrogenation synthesizing alcohol of claim 1-3, it is characterized in that catalyst applications in fixed-bed tube reactor, reducing condition is: with catalyst at H
2Under the atmosphere, be elevated to 400-600 ℃ of reduction 3-8 hour, H with the heating rate of 0.5-3 ℃/min
2Gas space velocity GHSV=1500-9000 h
-1Reaction condition is: in the 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07173101A (en) * | 1993-10-25 | 1995-07-11 | Tosoh Corp | Production of benzyl acetate |
| CN102085479A (en) * | 2009-12-02 | 2011-06-08 | 中国科学院大连化学物理研究所 | Catalyst for hydro-conversion of mixed aqueous solution containing alcohol, aldehyde, acid and ester into alcohols |
| CN102211201A (en) * | 2011-05-16 | 2011-10-12 | 西安交通大学 | Method for preparing Pt, Pd and Pt-M (M is Cu, Ag and Pd) alloy nanoparticles |
-
2012
- 2012-03-07 CN CN 201210057568 patent/CN102614914B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07173101A (en) * | 1993-10-25 | 1995-07-11 | Tosoh Corp | Production of benzyl acetate |
| CN102085479A (en) * | 2009-12-02 | 2011-06-08 | 中国科学院大连化学物理研究所 | Catalyst for hydro-conversion of mixed aqueous solution containing alcohol, aldehyde, acid and ester into alcohols |
| CN102211201A (en) * | 2011-05-16 | 2011-10-12 | 西安交通大学 | Method for preparing Pt, Pd and Pt-M (M is Cu, Ag and Pd) alloy nanoparticles |
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| 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 |
| CN109420492A (en) * | 2017-08-22 | 2019-03-05 | 湖南长岭石化科技开发有限公司 | A kind of hydrogenation catalyst and its preparation method and application and a kind of method of phenols hydrogenation reaction |
| 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 |
| CN108435174A (en) * | 2018-04-27 | 2018-08-24 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and preparation method and application of processing high concentrated organic wastewater |
| CN112371173A (en) * | 2020-11-27 | 2021-02-19 | 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 |
| 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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