CN105646148A - Method for preparing ethanol by hydrogenating acetic acid - Google Patents

Abstract

The invention discloses a method for preparing ethanol by hydrogenating acetic acid. The method comprises the following steps of mixing the acetic acid and hydrogen under the conditions that the temperature is 250 to 400DEG C, the pressure is 0.5 to 10.0MPa, the weight hourly space velocity is 0.2 to 8.0h<-1>, and the feeding mole ratio of the hydrogen to the acetic acid is 1:1 to 20:1; performing contact reaction on a mixture and a loaded transition metal carbide catalyst; hydrogenating the acetic acid to prepare the ethanol. The method disclosed by the invention has the advantages that the process flow is simple, the price of the catalyst is lower, the performance stability of the catalyst is good, and the stable operation time of the device is long; frequent switching operation of reaction and regeneration of a reactor can be avoided, the catalyst can be regenerated, posttreatment of a large amount of waste catalysts can be avoided, and further the influence on the environment is little.

Description

A kind of method of acetic acid hydrogenation ethanol

(1) technical field

A kind of method that the present invention relates to acetic acid hydrogenation ethanol, the method for especially a kind of supported transition metal carbide catalyst acetic acid hydrogenation ethanol.

(2) background technology

Ethanol is the liquid fuel of a kind of high-quality, sulphur content and ash are relatively low, combustibility is similar to gasoline, there is high oxygen content and octane number, relatively regular gasoline burning is complete, CO emission is low, using ethanol petrol can significantly decrease the environmental pollution that burns gasoline causes, ethanol is referred to as 21 century " green energy resource ". Along with oil supply and demand aggravation of contradictions, ambient pressure is day by day heavy, countries in the world common concern fungible energy source, has promoted the development of alcohol fuel. Existing alcohol production technology, mostly with crops for raw material, is subject to the restriction of raw material, and production cost is higher, it is difficult to meet the demand of alcohol fuel. Acetic acid catalysis hydrogenation is the feasible path of ethanol production, is also by the effective way of the indirect preparing liquid fuel of coal. Along with Development of Coal Chemical Industry, supply exceed demand for acetic acid. Alcohol production problem can not only be solved by acetic acid hydrogenation ethanol, moreover it is possible to the problem effectively solving acetic acid production capacity surplus, thus this technique has become the focus of research both at home and abroad.

Hydrogenation catalyst and reaction process about acetic acid hydrogenation ethanol have carried out big quantity research both at home and abroad. Hydrogenation catalyst mainly adopts load type palladium or platinum catalyst, load type palladium containing other metals or platinum catalyst and copper loaded catalyst. Owing to palladium and platinum are that noble metal, load type palladium or platinum catalyst are expensive, alcohol production is relatively costly. Further, since copper loaded catalyst less stable, this catalyst is difficult to commercial Application. Development cost is low, the non-noble metal hydrogenation catalyst of stable performance and acetic acid hydrogenation technique are important developing direction.

In transition metal carbide, carbon changes the surface electronic characteristic of transition metal, so as to have the performance similar with platinum, is a kind of non-noble metal hydrogenation catalyst active component. Transition metal carbide is little because of specific surface area, and its catalytic performance is poor. By its load on the porous material, prepare loaded catalyst, be the effective way of increasing specific surface area. The performance of load hydrogenation catalyst is affected by catalytic active component load capacity and the degree of scatter on carrier.

Incipient impregnation method is adopted to prepare loaded catalyst, it is possible to effectively utilize catalytic active component. In process on impregnating metal source to carrier, by adding chelating agent in dipping solution, improve source metal degree of scatter on carrier, increase metal surface area, improve the high active of hydrogenation catalysis of loaded catalyst. It addition, in source metal dipping process, utilize hyperacoustic peptizaiton, improve source metal degree of scatter on carrier, improve the catalysis activity of loaded catalyst. Utilizing on these method processabilities good transition metal carbide loaded catalyst basis, exploitation acetic acid hydrogenation ethanol technology has good using value.

(3) summary of the invention

A kind of method that it is an object of the present invention to provide acetic acid hydrogenation ethanol, namely by the method for supported transition metal carbide catalyst acetic acid hydrogenation ethanol, solves load type palladium or the high problem of expensive the caused alcohol production cost of platinum catalyst.

The technical solution used in the present invention is:

The present invention provides a kind of method of supported transition metal carbide catalyst acetic acid hydrogenation ethanol, and described method is: at temperature 250��400 DEG C, pressure 0.5��10.0MPa, mass space velocity 0.2��8.0 hour^-1, hydrogen and acetic acid feed amount of substance ratio 1:1��20:1 when, acetic acid and hydrogen are mixed, contact with supported transition metal carbide catalyst and carry out hydrogenation reaction, it is thus achieved that ethanol; Regenerate after catalysqt deactivation, recycle;

Described supported transition metal carbide catalyst is with transition metal carbide for active component, and with silicon oxide or aluminium oxide for carrier, described transition metal carbide mass loading amount is 1%��20%;

Described transition metal carbide is one or more mixture in carbonization nickel, molybdenum carbide, cobalt carbide, tungsten carbide.

Further, described aluminium oxide is Al₂O₃Or ��-Al₂O₃; Described silicon oxide is Bio-sil, it is preferable that the ZCX-2 type of Qingdao Haiyang chemical company production, 20��40 order Bio-sils.

Further, described hydrogenation conditions is temperature 280��380 DEG C, pressure 0.5��5.0MPa, feedstock quality air speed 0.5��5.0 hour^-1, hydrogen and acetic acid feed mol ratio 2:1��10:1, it is most preferred that temperature 300��350 DEG C, pressure 2.0��5.0MPa, feedstock quality air speed 0.5��2.0 hour^-1, hydrogen and acetic acid feed mol ratio 5:1��10:1.

Further, described transition metal carbide mass loading amount is 5%��15%.

Supported transition metal carbide catalyst of the present invention adopts incipient impregnation method to prepare: made dipping solution by transition metal with distilled water, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water, at room temperature it is stirred impregnating to catalyst carrier with dipping solution, room temperature stands 3��24h (preferably 5��8h), dry 3��24h (preferably 80��95 DEG C of dry 5��8h) at 60��100 DEG C of temperature; It is warmed up to 400 DEG C��700 DEG C, roasting 1��10h (preferably 1��5 DEG C/min is warmed up to 450 DEG C��650 DEG C, roasting 1��5h), it is thus achieved that catalyst precursor with 1��10 DEG C/min rate program; Then, catalyst precursor is loaded in tubular reactor, using pentane as carbon source, pass into hydrogen, at pressure 0.1��5.0MPa, pentane mass space velocity 0.2��2.0h^-1, hydrogen and when pentane volume ratio 100��1000:1, with 1��10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C��750 DEG C, constant temperature 1��10h (preferably 0.5��5.0MPa, 0.5��2.0h^-1, volume ratio 300��800:1 when, with 1��5 DEG C/min ramp to 500 DEG C��650 DEG C, constant temperature 2��6h), carry out catalyst precursor carbonization treatment, obtain supported transition metal carbide catalyst; In described dipping solution, transiting metal concentration is 1.0 �� 10^-5��9.0 �� 10^-3Mol/mL (preferably 4.3 �� 10^-5��1.3 �� 10^-3Mol/mL), described dipping solution volumetric usage is calculated as 0.5��5.5mL/g (preferably 0.8��1.5mL/g) with carrier quality.

Supported transition metal carbide catalyst of the present invention can also adopt complexation dipping method to prepare: is prepared dipping solution by transition metal, citric acid and distilled water, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water, at room temperature it is stirred impregnating to catalyst carrier with dipping solution, room temperature stands 3��24h (preferably 5��8h), dry 3��24h (preferably 80��95 DEG C of dry 5��8h) at 60��100 DEG C of temperature;It is warmed up to 400 DEG C��700 DEG C, roasting 1��10h (preferably 1��5 DEG C/min is warmed up to 450 DEG C��650 DEG C, roasting 1��5h), it is thus achieved that catalyst precursor with 1��10 DEG C/min rate program; Then, catalyst precursor is loaded in tubular reactor, using pentane as carbon source, pass into hydrogen, at pressure 0.1��5.0MPa, pentane mass space velocity 0.2��2.0h^-1, hydrogen and when pentane volume ratio 100��1000:1, with 1��10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C��750 DEG C, constant temperature 1��10h (preferably 0.5��5.0MPa, 0.5��2.0h^-1, volume ratio 300��800:1 when, with 1��5 DEG C/min ramp to 500 DEG C��650 DEG C, constant temperature 2��6h), carry out catalyst precursor carbonization treatment, obtain supported transition metal carbide catalyst, in described dipping solution, citric acid is 1:1��4:1 with the mol ratio of transition metal, and in described dipping solution, transiting metal concentration is 1.0 �� 10^-5��9.0 �� 10^-3Mol/mL (preferably 4.3 �� 10^-5��1.3 �� 10^-3Mol/mL), described dipping solution volumetric usage is calculated as 0.5��5.5mL/g (preferably 0.8��1.5mL/g) with carrier quality.

Supported transition metal carbide catalyst of the present invention can also adopt ultrasonic immersing method to prepare: is prepared dipping solution by transition metal and distilled water, dipping solution volume is 1��3 times of catalyst carrier maximum adsorption water volume, at room temperature it is stirred impregnating to catalyst carrier with dipping solution, after adding dipping solution, supersound process 10��60min (preferably 40��80W, 15��40min) when room temperature, ultrasonic power 30��100W; Room temperature stands 3��24h (preferably 5��8h), dry 3��24h (preferably 80��95 DEG C of dry 5��8h) at 60��100 DEG C of temperature; It is warmed up to 400 DEG C��700 DEG C, roasting 1��10h (preferably 1��5 DEG C/min is warmed up to 450 DEG C��650 DEG C, roasting 1��5h), it is thus achieved that catalyst precursor with 1��10 DEG C/min rate program; Then, catalyst precursor is loaded in tubular reactor, using pentane as carbon source, pass into hydrogen, at pressure 0.1��5.0MPa, pentane mass space velocity 0.2��2.0h^-1, hydrogen and when pentane volume ratio 100��1000:1, with 1��10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C��750 DEG C, constant temperature 1��10h (preferably 0.5��5.0MPa, 0.5��2.0h^-1, volume ratio 300��800:1 when, with 1��5 DEG C/min ramp to 500 DEG C��650 DEG C, constant temperature 2��6h), carry out catalyst precursor carbonization treatment, obtain supported transition metal carbide catalyst; In described dipping solution, transiting metal concentration is 1.0 �� 10^-5��9.0 �� 10^-3Mol/mL (preferably 4.3 �� 10^-5��1.3 �� 10^-3Mol/mL), described dipping solution volumetric usage is calculated as 0.5��5.5mL/g (preferably 0.8��1.5mL/g) with carrier quality.

Further, the described transition metal source one or more mixture in nickel nitrate, ammonium molybdate, ammonium metatungstate, cobalt nitrate, it is preferable that ammonium metatungstate or ammonium molybdate.

Further, the renovation process of described supported transition metal carbide catalyst is off into acetic acid raw material, continues to pass into hydrogen, is 100��1000h in temperature 300 DEG C��600 DEG C, pressure 0.8��6.0MPa, hydrogen volume air speed^-1Under condition, decaying catalyst is reacted hydrogenation regeneration 3��24h in device.

Further, described reaction is to carry out in the reactor of two or more serial or parallel connections, the catalyst that in each reactor, filling is identical or different.

The present invention react adopt the optional fixing bed of reactor, expanded bed, fluid bed, stirred-tank reactor, and catalytic distillation reactor. Reaction unit can have multiple reactor to operate in parallel or series. Material in reactor can take upstriker, it would however also be possible to employ downstriker.

Having the advantages that of the method for a kind of acetic acid hydrogenation ethanol of the present invention:

(1) supported transition metal carbide catalyst price is relatively low, and alcohol production is less costly;

(2) catalyst activity good stability, the device stable operation time is long, can avoid reactor reaction and regenerate frequent handover operation;

(3) catalyst is renewable, can avoid a large amount of dead catalyst post processing, and environmental effect is little.

(4) detailed description of the invention

Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to that:

Carrying alumina production procedure is by 30 grams of monohydrate aluminas (Shandong Aluminum Co., Ltd. group company), 3 grams of field mountain valley with clumps of trees and bamboo powder mix homogeneously, add 18 grams of distilled water and 21 gram mass marks are the aqueous solution of nitric acid of 5%, it is kneaded into walk, extruded moulding, dry rear temperature programming to 550 DEG C roasting 4 hours, size-reduced, sieve takes 20��40 granules, obtains Al₂O₃Carrier. Through above-mentioned extruded moulding, drying rear temperature programming to 850 DEG C roasting 4 hours, size-reduced, sieve takes 20��40 order granules, obtains ��-Al₂O₃Carrier.

SiO used in embodiment₂For Qingdao Haiyang chemical company produce ZCX-2 type, 20��40 order Bio-sils, in liquid volume with solid masses than under 50:1 (mL/g), 80 DEG C of conditions of temperature, with the aqueous solution of nitric acid of mass concentration 10%, it is processed 8h, isolated by filtration; Filter cake under liquid volume and solid masses are than 50:1 (mL/g), 80 DEG C of conditions of temperature through No. 2 distilled water agitator treating 3h, isolated by filtration, 120 DEG C of dry 3h, again respectively through 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C roasting 1h, obtain the SiO processed₂, as catalyst carrier.

Nickel nitrate (Ni (NO used₃)₂��6H₂O), ammonium molybdate ((NH₄)₆Mo₇O₂₄��4H₂O), ammonium metatungstate ((NH₄)₆H₂W₁₂O₄₀��nH₂O), cobalt nitrate (Co (NO₃)₂��6H₂O), citric acid, pentane is all purchased from the chemically pure reagent of Chemical Reagent Co., Ltd., Sinopharm Group. Hydrogen is from Hangzhou Jin Gong special gas company limited, purity > 99.99%.

Adopting fixed-bed reactor to carry out acetic acid hydrogenation reaction experiment, rustless steel tubular type reactor size is: internal diameter 10mm, external diameter 14mm, long 100cm, and by Catalyst packing portion in the reactor, inert stone sand is filled up at reactor two ends. Reaction temperature, by temperature control instrument control, is regulated hydrogenation reaction pressure by counterbalance valve.

With Japan's Shimadzu GC-2014C chromatographic product composition, chromatographic detector is thermal conductivity detector (TCD), chromatographic column is the GDX-102 packed column of 2m �� 4mm, injector temperature is 140 DEG C, column temperature is 120 DEG C, detector temperature is 130 DEG C, and chromatographic data processing method is rectification area normalization method. Product contains unconverted acetic acid (HAc), ethanol (EtOH), ethyl acetate (EtOAc), acetone (Acetone), acetaldehyde (Acetal), the amount (T of relative acetic acid total organic matter in product₀) it is:

$T_0={\mathrm{\&lambda;}}_{HAc}\&times;\frac{A_{HAc}}{M_{HAc}}+{\mathrm{\&lambda;}}_{EtOH}\&times;\frac{A_{EtOH}}{H_{EtOH}}+2\&times;{\mathrm{\&lambda;}}_{EtOAc}\&times;\frac{A_{EtOAc}}{M_{EtOAc}}+1.5\&times;{\mathrm{\&lambda;}}_{Acetone}\&times;\frac{A_{Acetone}}{M_{Acetone}}+\frac{A_{Acetal}}{M_{Acetal}}---\left(1\right)$

Acetic acid conversion (X) is:

$X=(1-{\mathrm{\&lambda;}}_{HAc}\&times;\frac{A_{HAc}}{M_{HAc}\&CenterDot;T_0})\&times;100\%---\left(2\right)$

Ethanol selectivity (S_EtOH) it is:

$S_{EtOH}=\frac{{\mathrm{\&lambda;}}_{EtOH}\&times;\frac{A_{EtOH}}{M_{EtOH}}}{T_0-{\mathrm{\&lambda;}}_{HAc}\&times;\frac{A_{HAc}}{M_{HAc}}}\&times;100\%---\left(3\right)$

Ethyl acetate selectivity (S_EtOAc) it is:

$S_{EtOAc}=\frac{2\&times;{\mathrm{\&lambda;}}_{EtOAc}\&times;\frac{A_{EtOAc}}{M_{EtOAc}}}{T_0-{\mathrm{\&lambda;}}_{HAc}\&times;\frac{A_{HAc}}{M_{HAc}}}\&times;100\%---\left(4\right)$

Acetone selectivity (S_Acetone) it is:

$S_{Acetone}=\frac{1.5\&times;{\mathrm{\&lambda;}}_{Acetone}\&times;\frac{A_{Acetone}}{M_{Acetone}}}{T_0-{\mathrm{\&lambda;}}_{HAc}\&times;\frac{A_{HAc}}{M_{HAc}}}\&times;100\%---\left(5\right)$

Acetaldehyde selectivity (S_Acetal) it is:

$S_{Acetal}=\frac{\frac{A_{Acetal}}{M_{Acetal}}}{T_0-{\mathrm{\&lambda;}}_{HAc}\&times;\frac{A_{HAc}}{M_{HAc}}}\&times;100\%---\left(6\right)$

In formula, A_iRate, M is divided for i component color area under spectrum_iFor i component molar quality;��_iFor i component chromatograph correction factor, wherein ��_HAc=1.0208, ��_EtOH=1.3158, ��_EtOAc=2.9321, ��_Acetone=0.9763.

Room temperature of the present invention refers to 25 DEG C.

Embodiment 1:1%WC/SiO₂Catalyst preparing

(its specific surface area is 480m to weigh the Bio-sil carrier of 10g²/ g), by 0.13g (4.3974 �� 10^-5Mol) 12mL dipping solution prepared by ammonium metatungstate and distilled water, and its tungsten concentration is 4.3974 �� 10^-5Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 3h, dry 3h at 90 DEG C of temperature; It is warmed up to 400 DEG C, roasting 10h with 1 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 0.1MPa, pentane mass space velocity 0.2h^-1, hydrogen and when pentane volume ratio 100:1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C, constant temperature 10h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 1%, be designated as 1%WC/SiO₂��

Embodiment 2:5%WC/SiO₂Catalyst preparing

Weigh the Bio-sil carrier of 10g, by 0.65g (2.1987 �� 10^-4Mol) 12mL dipping solution prepared by ammonium metatungstate and distilled water, and its tungsten concentration is 2.1987 �� 10^-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 24h, dry 24h at 60 DEG C of temperature; It is warmed up to 700 DEG C, roasting 1h with 2 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 0.5MPa, pentane mass space velocity 0.5h^-1, hydrogen and when pentane volume ratio 500:1, with 5 DEG C/min speed from 100 DEG C of temperature programmings to 550 DEG C, constant temperature 6h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 5%, be designated as 5%WC/SiO₂��

Embodiment 3:10%WC/SiO₂Catalyst preparing

Weigh the Bio-sil carrier of 10g, by 1.3g (4.3974 �� 10^-4Mol) 12mL dipping solution prepared by ammonium metatungstate and distilled water, and its tungsten concentration is 4.3974 �� 10^-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 6h, dry 12h at 80 DEG C of temperature; It is warmed up to 650 DEG C, roasting 4h with 5 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 5.0MPa, pentane mass space velocity 2.0h^-1, hydrogen and when pentane volume ratio 1000:1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 10%, be designated as 10%WC/SiO₂��

Embodiment 4:20%WC/SiO₂Catalyst preparing

Weigh the Bio-sil carrier of 10g, by 2.6g (8.7948 �� 10^-4Mol) 12mL dipping solution prepared by ammonium metatungstate and distilled water, and its tungsten concentration is 8.7948 �� 10^-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water.Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 4h, dry 3h at 100 DEG C of temperature; It is warmed up to 600 DEG C, roasting 6h with 10 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 5.0MPa, pentane mass space velocity 2.0h^-1, hydrogen and when pentane volume ratio 500:1, with 5 DEG C/min speed from 100 DEG C of temperature programmings to 550 DEG C, constant temperature 6h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 20%, be designated as 20%WC/SiO₂��

Embodiment 5:10%WC/ ��-Al₂O₃Catalyst preparing

Weigh the ��-Al of 10g₂O₃(its specific surface area is 296m to carrier²/ g), by 1.3g (4.3974 �� 10^-4Mol) 8mL dipping solution prepared by ammonium metatungstate and distilled water, and its tungsten concentration is 6.5961 �� 10^-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 8mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 24h, dry 24h at 60 DEG C of temperature; It is warmed up to 700 DEG C, roasting 1h with 2 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 0.5MPa, pentane mass space velocity 0.5h^-1, hydrogen and when pentane volume ratio 500:1, with 5 DEG C/min speed from 100 DEG C of temperature programmings to 550 DEG C, constant temperature 6h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 10%, be designated as 10%WC/ ��-Al₂O₃��

Embodiment 6:10%WC/Al₂O₃Catalyst preparing

Weigh the Al of 10g₂O₃(its specific surface area is 302m to carrier²/ g), by 1.3g (4.3974 �� 10^-4Mol) 8mL dipping solution prepared by ammonium metatungstate and distilled water, and its tungsten concentration is 6.5961 �� 10^-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 8mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 24h, dry 24h at 60 DEG C of temperature; It is warmed up to 700 DEG C, roasting 1h with 2 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 0.5MPa, pentane mass space velocity 0.5h^-1, hydrogen and when pentane volume ratio 500:1, with 5 DEG C/min speed from 100 DEG C of temperature programmings to 550 DEG C, constant temperature 6h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 10%, be designated as 10%WC/Al₂O₃��

Embodiment 7:10%Ni₂C/SiO₂Catalyst preparing

Using Bio-sil as carrier, with Ni (NO₃)₂��6H₂O is as nickel source. Weigh the Bio-sil of 10g, by 4.5g (1.5474 �� 10^-2Mol) Ni (NO₃)₂��6H₂12mL dipping solution prepared by O and distilled water, and its nickel concentration is 1.2895 �� 10^-3Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 5h, dry 24h at 90 DEG C of temperature;It is warmed up to 650 DEG C, roasting 4h with 5 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 1.0MPa, pentane mass space velocity 2.0h^-1, hydrogen and when pentane volume ratio 1000:1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 10%, be designated as 10%Ni₂C/SiO₂��

Embodiment 8:10%MoC/SiO₂Catalyst preparing

Using Bio-sil as carrier, with (NH₄)₆Mo₇O₂₄��4H₂O is as molybdenum source. Weigh the Bio-sil of 10g, by 1.64g (1.327 �� 10^-3Mol) (NH₄)₆Mo₇O₂₄��4H₂12mL dipping solution prepared by O and distilled water, and its molybdenum concentration is 7.7409 �� 10^-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 5h. Dry 24h at 60 DEG C of temperature; It is warmed up to 650 DEG C, roasting 10h with 5 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 1.0MPa, pentane mass space velocity 2.0h^-1, under hydrogen and pentane volume ratio 1000 condition, with 2 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of molybdenum carbide load quality mark 10%, be designated as 10%MoC/SiO₂��

Embodiment 9:10%Co₂C/SiO₂Catalyst preparing

Using Bio-sil as carrier, with Co (NO₃)₂��6H₂O is as cobalt source. Weigh the Bio-sil of 10g, by 4.48g (1.5391 �� 10^-2Mol) Co (NO₃)₂��6H₂12mL dipping solution prepared by O and distilled water, and its cobalt concentration is 1.2826 �� 10^-3Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 5h. Dry 6h at 90 DEG C of temperature; It is warmed up to 650 DEG C, roasting 10h with 5 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 1.0MPa, pentane mass space velocity 2.0h^-1, under hydrogen and pentane volume ratio 1000 condition, with 2 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of cobalt carbide load quality mark 10%, be designated as 10%Co₂C/SiO₂��

Embodiment 10:10%WC/SiO₂-L1 catalyst preparing

Weigh the Bio-sil carrier of 10g, by 1.3g (4.3974 �� 10^-4Mol) ammonium metatungstate, 1.1089g (5.277 �� 10^-3Mol) 12mL dipping solution prepared by citric acid and distilled water, and its tungsten and citric acid concentration are 4.3974 �� 10^-4Mol/mL, in dipping solution, citric acid is 1:1 with the mol ratio of tungsten in ammonium metatungstate, and dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 6h, dry 12h at 80 DEG C of temperature; It is warmed up to 650 DEG C, roasting 4h with 5 DEG C/min rate program.Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 1.0MPa, pentane mass space velocity 2.0h^-1, hydrogen and when pentane volume ratio 1000:1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 10%, be designated as 10%WC/SiO₂-L1��

Embodiment 11:10%WC/SiO₂-L4 catalyst preparing

Weigh the Bio-sil carrier of 10g, by 1.3g (4.3974 �� 10^-4Mol) ammonium metatungstate, 4.4356g (2.1108 �� 10^-2Mol) 12mL dipping solution prepared by citric acid and distilled water, its tungsten and citric acid concentration respectively 4.3974 �� 10^-4Mol/mL and 1.759 �� 10^-3Mol/mL, in dipping solution, citric acid is 4:1 with the mol ratio of tungsten in ammonium metatungstate, and dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. Carry out room temperature immersion by incipient impregnation method, in 10g carrier, drip 12mL dipping solution, and be stirred continuously. After dropwising, room temperature stands 6h, dry 12h at 80 DEG C of temperature; It is warmed up to 650 DEG C, roasting 4h with 5 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 1.0MPa, pentane mass space velocity 2.0h^-1, hydrogen and when pentane volume ratio 1000:1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 10%, be designated as 10%WC/SiO₂-L4��

Embodiment 12:10%WC/SiO₂-U30 catalyst preparing

Weigh the Bio-sil carrier of 10g, by 1.3g (4.3974 �� 10^-4Mol) 12mL dipping solution prepared by ammonium metatungstate and distilled water, and its tungsten concentration is 4.3974 �� 10^-4Mol/mL, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water. In the KQ-100DE type numerical control ultrasonic cleaner that Kunshan Ultrasonic Instruments Co., Ltd. produces, in room temperature beaker, drip 17mL dipping solution to 10g carrier, and be stirred continuously; After adding dipping solution, the supersound process 60min when room temperature, supersonic frequency 40kHz, ultrasonic power 30W; Room temperature stands 6h, dry 12h at 80 DEG C of temperature; It is warmed up to 650 DEG C, roasting 4h with 5 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 1.0MPa, pentane mass space velocity 2.0h^-1, hydrogen and when pentane volume ratio 1000:1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 10%, be designated as 10%WC/SiO₂-U30��

Embodiment 13:10%WC/SiO₂-U100 catalyst preparing

Weigh the Bio-sil carrier of 10g, by 1.3g (4.3974 �� 10^-4Mol) 36mL dipping solution prepared by ammonium metatungstate and distilled water, and its tungsten concentration is 1.4658 �� 10^-4Mol/mL, dipping solution volume is 3 times of catalyst carrier maximum adsorption water volume. In the KQ-100DE type numerical control ultrasonic cleaner that Kunshan Ultrasonic Instruments Co., Ltd. produces, in room temperature beaker, drip 36mL dipping solution to 10g carrier, and be stirred continuously;After adding dipping solution, the supersound process 10min when room temperature, supersonic frequency 40kHz, ultrasonic power 100W; Room temperature stands 6h, dry 12h at 80 DEG C of temperature; It is warmed up to 650 DEG C, roasting 4h with 5 DEG C/min rate program. Then, dry catalyst precursor is loaded in tubular reactor, using pentane as carbon source, passes into hydrogen, at pressure 1.0MPa, pentane mass space velocity 2.0h^-1, hydrogen and when pentane volume ratio 1000:1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain the loaded catalyst of Tungsten Carbides mass fraction 10%, be designated as 10%WC/SiO₂-U100��

Embodiment 14: catalyst performance evaluation

Adopt fixed-bed reactor, at temperature 320 DEG C, pressure 2.0MPa, quality of acetic acid air speed 0.5h^-1, hydrogen and acetic acid feed mol ratio 10:1 reaction condition under, carry out acetic acid hydrogenation reaction with the catalyst of above-mentioned preparation, evaluate the catalytic performance of catalyst, experimental result is listed in table 1.

The acetic acid hydrogenation reaction result of the various catalyst of table 1

As it can be seen from table 1 along with catalyst transition metal carbide load capacity increases, acetic acid conversion is gradually increased, and catalyst hydrogenation catalysis activity gradually steps up, and ethanol selectivity increases to some extent, and ethyl acetate, acetone and acetaldehyde selectivity all decrease. When transition metal carbide load quality mark is 10%, with SiO₂Catalyst activity and ethanol selectivity for carrier are somewhat quite a lot of. Relatively transition metal carbide load quality mark is the catalyst performance of 10%, and catalyst activity order from high to low is WC, MoC, Co₂C��Ni₂C, ethanol selectivity order from high to low is MoC, Co₂C��Ni₂C, WC. On the whole, the catalytic performance of WC loaded catalyst is better. Prepare the acetic acid conversion of catalyst by complexation infusion process and ultrasonic immersing method and ethanol selectivity is all better than catalyst prepared by equi-volume impregnating, and along with citric acid complexing agent consumption and ultrasonic power increase, catalyst performance makes moderate progress. On the whole, acetone and acetaldehyde selectivity numerical value are less, and ethanol selectivity is more than 80%.

Embodiment 15: hydrogenation conditions is investigated

Adopt fixed-bed reactor, at 10%WC/SiO₂Under catalyst action, carrying out the acetic acid hydrogenation reaction of different condition, the reaction condition impact of single factor exploration temperature, pressure, mass space velocity, hydrogen and acetic acid feed mol ratio, experimental result is in Table 2. As known from Table 2, along with reaction temperature raising, pressure increases, mass space velocity reduces, hydracid mol ratio increases, and acetic acid conversion and ethanol selectivity all increase, and ethyl acetate selectivity reduces, this illustrates, strengthening hydrogenation conditions is conducive to acetic acid to be converted into ethanol.

The experimental result of hydrogenation conditions impact investigated by table 2

Embodiment 16: catalyst performance stabilised is investigated

Adopt fixed-bed reactor, at 10%WC/SiO₂Under catalyst action, at temperature 350 DEG C, pressure 5.0MPa, mass space velocity 0.5h^-1, hydracid mol ratio 5:1 reaction condition under, carry out acetic acid hydrogenation sustained response, investigate the stability of catalyst, experimental result is in Table 3. From table 3 it can be seen that be performed continuously over the acetic acid hydrogenation reaction of 1000h under determining reaction condition, acetic acid conversion and each selectivity of product are basically unchanged, and illustrate that catalyst has good stability.

The investigation result of table 3 catalyst activity stability

Embodiment 17: hydrogenation catalyst regeneration and performance evaluation thereof

Adopt fixed-bed reactor, at 10%WC/SiO₂Under catalyst action, at temperature 350 DEG C, pressure 5.0MPa, mass space velocity 0.5h^-1, hydracid mol ratio 5:1 reaction condition under be performed continuously over acetic acid hydrogenation reaction, when acetic acid conversion is reduced to 90%, stop input acetic acid raw material;Continue to pass into hydrogen, enter decaying catalyst hydrogenation regeneration stage, at pressure 5.0MPa, hydrogen volume air speed 200h^-1Under condition, temperature is increased to 400 DEG C of constant temperature hydrogenation regeneration 3h, then temperature is brought up to 500 DEG C of constant temperature regeneration 24h. Then, at temperature 350 DEG C, pressure 5.0MPa, mass space velocity 0.5h^-1, hydracid mol ratio 5:1 reaction condition under input acetic acid and hydrogen, be performed continuously over catalytic hydrogenation reaction, result is listed in table 4.

The performance evaluation of table 4 regeneration catalyzing agent

As known from Table 4, decaying catalyst is through hydrogenation regenerative operation, and acetic acid conversion brings up to 99.22% from 90%. This illustrates, inactivation loaded catalyst is through hydrogenation regeneration, and catalyst activity is substantially recovered. Comparison sheet 3 and table 4 data are it can be seen that activity stability and the selectivity of product of regeneration catalyzing agent are all suitable with fresh catalyst.

Above-mentioned test result indicate that, acetic acid can be converted into ethanol by the catalytic hydrogenation reaction method of the present invention effectively, and the high active of hydrogenation catalysis of catalyst and reaction selectivity are all higher, and activity stability is good, and can regenerate. The inventive method is the effective ways of acetic acid hydrogenation ethanol, has using value.

Claims (10)

1. the method for an acetic acid hydrogenation ethanol, it is characterised in that described method is: at temperature 250��400 DEG C, pressure 0.5��10.0MPa, mass space velocity 0.2��8.0 hour^-1, hydrogen and acetic acid feed amount of substance ratio 1:1��20:1 when, acetic acid and hydrogen are mixed, contact with supported transition metal carbide catalyst and carry out hydrogenation reaction, it is thus achieved that ethanol; Regenerate after catalysqt deactivation, recycle;

Described supported transition metal carbide catalyst is with transition metal carbide for active component, and with silicon oxide or aluminium oxide for carrier, described transition metal carbide mass loading amount is 1%��20%;

Described transition metal carbide is one or more mixture in carbonization nickel, molybdenum carbide, cobalt carbide, tungsten carbide.

2. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterised in that described aluminium oxide is Al₂O₃Or ��-Al₂O₃; Described silicon oxide is Bio-sil.

3. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterised in that described hydrogenation conditions is temperature 280��380 DEG C, pressure 0.5��5.0MPa, feedstock quality air speed 0.5��5.0 hour^-1, hydrogen and acetic acid feed mol ratio 2:1��10:1.

4. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterised in that described transition metal carbide mass loading amount is 5%��15%.

5. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterized in that described supported transition metal carbide catalyst adopts incipient impregnation method to prepare: made dipping solution by transition metal with distilled water, at room temperature it is stirred impregnating to carrier with dipping solution, room temperature stands 3��24h, dry 3��24h at 60��100 DEG C of temperature; It is warmed up to 400 DEG C��700 DEG C, roasting 1��10h, it is thus achieved that catalyst precursor with 1��10 DEG C/min rate program; Then, catalyst precursor is loaded in tubular reactor, using pentane as carbon source, pass into hydrogen, at pressure 0.1��5.0MPa, pentane mass space velocity 0.2��2.0h^-1, hydrogen and when pentane volume ratio 100��1000:1, with 1��10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C��750 DEG C, constant temperature 1��10h, obtain supported transition metal carbide catalyst;In described dipping solution, transiting metal concentration is 1.0 �� 10^-5��9.0 �� 10^-3Mol/mL, described dipping solution volumetric usage is calculated as 0.5��5.5mL/g with carrier quality.

6. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterized in that described supported transition metal carbide catalyst adopts the preparation of complexation dipping side: prepared dipping solution by transition metal, citric acid and distilled water, at room temperature it is stirred impregnating to carrier with dipping solution, room temperature stands 3��24h, dry 3��24h at 60��100 DEG C of temperature; It is warmed up to 400 DEG C��700 DEG C, roasting 1��10h, it is thus achieved that catalyst precursor with 1��10 DEG C/min rate program; Then, catalyst precursor is loaded in tubular reactor, using pentane as carbon source, pass into hydrogen, at pressure 0.1��5.0MPa, pentane mass space velocity 0.2��2.0h^-1, hydrogen and when pentane volume ratio 100��1000:1, with 1��10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C��750 DEG C, constant temperature 1��10h, obtain supported transition metal carbide catalyst; In described dipping solution, citric acid is 1:1��4:1 with the ratio of the amount of substance of transition metal, and in described dipping solution, transiting metal concentration is 1.0 �� 10^-5��9.0 �� 10^-3Mol/mL, described dipping solution volumetric usage is calculated as 0.5��5.5mL/g with carrier quality.

7. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterized in that described supported transition metal carbide catalyst adopts ultrasonic immersing method to prepare: prepared dipping solution by transition metal and distilled water, at room temperature it is stirred impregnating to carrier with dipping solution, after adding dipping solution, supersound process 10��60min when room temperature, ultrasonic power 30��100W; Room temperature stands 3��24h, dry 3��24h at 60��100 DEG C of temperature; It is warmed up to 400 DEG C��700 DEG C, roasting 1��10h, it is thus achieved that catalyst precursor with 1��10 DEG C/min rate program; Then, catalyst precursor is loaded in tubular reactor, using pentane as carbon source, pass into hydrogen, at pressure 0.1��5.0MPa, pentane mass space velocity 0.2��2.0h^-1, hydrogen and when pentane volume ratio 100��1000:1, with 1��10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C��750 DEG C, constant temperature 1��10h, carry out catalyst precursor carbonization treatment, obtain supported transition metal carbide catalyst; In described dipping solution, transiting metal concentration is 1.0 �� 10^-5��9.0 �� 10^-3Mol/mL, described dipping solution volumetric usage is calculated as 0.5��5.5mL/g with carrier quality.

8. the method for acetic acid hydrogenation ethanol as described in one of claim 5��7, it is characterised in that the described transition metal source one or more mixing in nickel nitrate, ammonium molybdate, ammonium metatungstate, cobalt nitrate.

9. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterized in that the renovation process of described supported transition metal carbide catalyst is off into acetic acid raw material, continue to pass into hydrogen, be 100��1000h in temperature 300 DEG C��600 DEG C, pressure 0.8��6.0MPa, hydrogen volume air speed^-1Under condition, decaying catalyst is reacted hydrogenation regeneration 3��24h in device.

10. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterised in that described reaction is to carry out in the reactor of two or more serial or parallel connections, the catalyst that in each reactor, filling is identical or different.