CN103055852B - Highly dispersed palladium/carbon nanometer tube catalyst for anthraquinone hydrogenation and preparation method thereof - Google Patents
Highly dispersed palladium/carbon nanometer tube catalyst for anthraquinone hydrogenation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a highly dispersed palladium/carbon nanometer tube catalyst for anthraquinone hydrogenation and a preparation method thereof, and relates to a catalyst and a preparation method. According to the invention, a carbon nanometer tube industrial product with good conductivity, heat conductivity, high mechanical strength and huge external specific surface is used as a palladium carrier; simultaneously ultrasonic is utilized to further enhance the dispersity and uniformity of palladium and the carbon nanometer tube; and a nanometer palladium catalyst uniformly loaded on the surface of the carbon nanometer tube is prepared in a slurry reactor by adopting a liquid phase reduction method. The catalyst needs no extrusion molding and can be directly suspended in the liquid phase for normal-pressure or pressurized hydrogenation of anthraquinone; the activity of the catalyst is not reduced after the catalyst is used for a plurality of times by filtration and separation; moisture, acid and alkaline do not influence the use effect; the catalytic activity of the new catalyst is 4-8 times higher than that of the traditional Pd/gamma-Al2O3 catalyst, and the amount of the catalyst used can be greatly reduced. The catalyst can be used for replacing the traditional catalyst, the post treatment of the traditional catalyst is simplified, the treatment capability of a device is greatly increased, and the operation cost is lowered.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method, particularly a kind of palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation and preparation method.
Background technology
Hydrogen peroxide is a kind of green chemical products, is widely used in the industries such as chemical industry, papermaking, environmental protection, electronics, food, medicine, weaving, mining industry, agricultural residue processing.The production method of current hydrogen peroxide is a lot, and wherein anthraquinone is produce the topmost method of hydrogen peroxide both at home and abroad, accounts for more than 95% of industrial total productive capacity.Anthraquinone hydrogenation is the core of anthraquinone technique.Load type palladium catalyst is current anthraquinone hydrogenation is the most also use catalyst the most widely, current industrial extensive use be Pd/ γ-Al
2o
3catalyst, but its activity is not high, requires higher to anthraquinone working solution, needs neutralization, the process such as dry, and catalyst itself exists the problems such as perishable, aging, inactivation and active component come off.Palladium belongs to rare precious metals, the height of catalyst activity and palladium load capacity becomes the key factor affecting Hydrogen Peroxide Production, because conventional catalyst activity is low, catalyst use amount is large, major part Pd active component is owing to containing in carrier inside, can not play a role well, and number of dropouts is large, reclaiming difficulty.Therefore, improving the activity of palladium catalyst, reduce the load capacity of palladium, is the dominant direction of catalyst research and development.
Notification number is that the Chinese invention patent of CN101804346A provides a kind of nano Pd catalyst for anthraquinone hydrogenation and preparation method.Its preparation methods steps mainly comprises preparation cape jasmine leachate, joins for mixed solution by palladium bichloride cape jasmine leachate, the nano Pd catalyst on cape jasmine must be carried on, it is characterized in that used carrier is CNT, active component is Pd nano particle, particle diameter 3 ~ 10 nanometer, palladium catalyst mass fraction is 1.2% ~ 3.6%; Palladium bichloride cape jasmine mixed solution palladium bichloride concentration used 1 ~ 2mmol/L in preparation process.This invention adopts cape jasmine as carrier, and the reduction of cape jasmine leachate prepares gained load type palladium catalyst, relative to Pd/ γ-Al
2o
3catalyst can reduce the use amount of palladium, and improve catalytic activity about 80% ~ 100%, visible palladium nanometer can significantly improve the catalytic activity of catalyst.
Notification number is carbon nanotube loaded palladium catalyst and the preparation method that the Chinese invention patent of CN101703930 provides a kind of cinnamic acid hydrogenation.Its preparation methods steps mainly comprises the preparation of palladium saline solution, adds CNT ultrasonic disperse, formaldehyde or NaBH
4reduction, filtration and drying obtain.This catalyst average grain diameter reaches 5 ~ 6nm.Although use CNT as carrier and Pd nano particle as active component, but because Pd concentration is high, reducing agent consumption is few, the problems such as the recovery time is short, the reduction effect of palladium active component is undesirable, this catalyst shows certain activity in cinnamic acid hydrogenating reduction process, but repeats the catalyst prepared of the method effect not obvious in anthraquinone hydrogenation system.
Summary of the invention
The technical problem to be solved in the present invention is: provide palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation that a kind of nanoparticle palladium consumption is few, catalytic efficiency is high and preparation method thereof.
The technical scheme solved the problems of the technologies described above is: a kind of palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation, this catalyst be a kind of in carbon nano tube surface the dispersed surface having nanoparticle palladium to be formed be hair shape, be mainly used in the palladium/carbon nano-tube catalyst of anthraquinone hydrogenation, the load capacity of described nanoparticle palladium is the 0.28wt% ~ 8.26wt% of CNT.
The particle diameter of described nanoparticle palladium is 2 ~ 4nm.
Another technical scheme of the present invention is: a kind of preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation: comprise the steps:
A. in reaction vessel, add CNT and water for 1:45 ~ 150 in mass ratio, be stirred to carbon nanotube dispersed even, obtained carbon nano tube suspension;
B. keep stirring, the 0.28wt% ~ 8.26wt% being CNT by the load capacity of nanoparticle palladium in the carbon nano tube suspension obtained in steps A slowly drips the palladium bichloride hydrochloric acid solution that concentration is 0.125 ~ 2g/L, obtains palladium ion/carbon nano tube suspension;
C. pH=9 ~ 12 that alkaline solution regulates palladium ion/carbon nano tube suspension are dripped in stepb;
D. under stirring, add excessive reducing agent, keep stirring, raised temperature to 40 ~ 60 DEG C, regulate and keep pH=
9 ~ 14carry out reduction reaction;
E. filter, wash and drying, obtain the high dispersive palladium/carbon nano-tube catalyst for anthraquinone hydrogenation.
Described stirring refers to and adopts mechanical agitation or adopt ultrasonic wave to stir or adopt machinery and ultrasonic wave jointly to stir.
Mixing time in described steps A is 20 ~ 30 minutes.
Interval time between step B and step C is 10 ~ 30 minutes.
Alkaline solution used in step C is the NaOH solution of 15 ~ 30wt%.
Reducing agent used is in step D formaldehyde, glucose or sodium formate.
Reduction reaction terminal described in step D is that the pH of palladium ion/carbon nano tube suspension no longer changes.
Described reaction vessel is slurry bed system or flask or stirred tank.
Owing to adopting technique scheme, the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the present invention and preparation method, compared with existing catalyst and preparation method, have following beneficial effect:
1. nanoparticle palladium consumption is few:
The present invention adopts CNT as carrier, because the Extra specific surface area of CNT is larger, can effectively reduce nanoparticle palladium containing in carrier inside, thus active component nanoparticle palladium is fully utilized, greatly reduce the consumption of nanoparticle palladium.
In addition, the present invention also uses mechanical agitation or ultrasonic wave to stir in preparation method, particularly ultrasonic wave stirs, the dispersion of active component can be strengthened, reduce the gathering of nanoparticle palladium, thus improve the effective rate of utilization of nanoparticle palladium, reduce further the use amount of nanoparticle palladium, make the consumption of nanoparticle palladium save more than 80%, and can hydrogenation efficiency be significantly improved on this basis.
2. catalytic efficiency is high:
Because the present invention adopts CNT as carrier, CNT is good catalytic hydrogenation auxiliary agent, can improve the catalytic effect of catalyst; In addition, the present invention by controlling palladium chloride solution concentration, reducing agent and reducing condition, can improve the reduction effect of active component nanoparticle palladium in preparation method, and improve the catalytic efficiency of catalyst, catalyst of the present invention is than conventional Pd/ γ-Al
2o
3catalyst activity is high 4 ~ 8 times, can up to 900 gH
2o
2(gPdh)
-1.
3. can carry out anthraquinone normal pressure and hydrogenation with pressure:
Carbon nanometer tube loaded type catalyst particle size prepared by the present invention is micron level, comparatively be adapted at carrying out hydrogenation reaction in suspension bed (slurry bed system) reactor, less particle is beneficial to suspension, particle is made to be suspended in reaction liquid uniformly, so the catalyst that the present invention is prepared into without shaping, can carry out anthraquinone normal pressure and hydrogenation with pressure in the liquid phase.
4. can time use, without the need to dehydration, dry during use:
CNT is originally as hydrophobic structure, more hydrophilic than being easier to, common suction filtration can remove most moisture, and in oleaginous system, catalyst easily contacts with reaction mass, and existing alumina catalyst is hydrophilic and consumption is large, must be dewatered guarantee reaction rate, experiment proof, adds water and the catalytic activity of acid adding to catalyst of the present invention does not reduce, therefore, catalyst of the present invention can time use, need not γ-Al during use
2o
3the steps such as the dehydration that loaded catalyst needs, drying and acid-base neutralization.
5. directly can use, not need activation, also acid and alkali affects and reduces active:
The effect of activation is 0 valency Pd by the Pd particle reduction of+divalent, and in the present invention, Kaolinite Preparation of Catalyst adopts the preparation of liquid-phase reduction method, and active component has been 0 valency Pd, and Here it is and adopt the difference of preparation catalyst, therefore need not activate; And alumina type supported catalyst is because carrier oxygenation efficiency is 2 property oxides, get final product and acid reaction, also can with alkali reaction, in Long-Time Service process, acid and alkali corrosion and washing away of liquid stream make active component peel off from carrier surface, therefore, catalyst of the present invention can directly use, and does not need activation, and also acid and alkali affects and reduces active.
6. range of application is more extensive:
Catalyst application scope of the present invention is comparatively extensive, both can use in reactor, tower, and also can apply in gas phase, solid system, also can be used for other hydrogenation system; The Pd/CNTs catalyst of gained of the present invention, can not only as the catalyst of anthraquinone hydrogenation, can also as the catalyst of other hydrogenation reactions.
7. preparation cost is low:
Catalyst of the present invention is through amplifying preparation, preparation 50g catalyst only needs 5L airlift reactor as container, and 50g catalyst at least needs the reaction vessel of 250L in the preparation method of existing disclosed catalyst, and reduction temperature catalytic amount that is high, that be prepared into is few in existing preparation method, waste energy, in the present invention, Kaolinite Preparation of Catalyst only needs a small amount of hydrochloric acid, water, NaOH and reducing agent, wherein reducing agent is the formaldehyde, sodium formate, glucose etc. that price is comparatively cheap, and reduction temperature only needs 40 ~ 60 DEG C; Greatly save the energy, reduce cost.
8. technique is simple, be suitable for industrial production:
Present invention process is simple, catalyst preparation process mild condition, and Palladium recovery is comparatively easy, can be widely used in industrial production.
Below, in conjunction with Figure of description and specific embodiment, the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the present invention and the technical characteristic of preparation method are further described.
accompanying drawing illustrates:
Fig. 1: be the XRD collection of illustrative plates (Fig. 1 is different palladium load capacity superposition XRD spectra, and for convenience of observing, portion diffracts spectrum ordinate has translation process) of Kaolinite Preparation of Catalyst and pure nano-carbon tube in the present embodiment 9,14,15 and 16;
In FIG, abscissa is the angle of diffraction 2 θ/degree, and ordinate is diffracted intensity Intensity(a.u.);
In Fig. 1,26.0 °, 43.0 ° and 44.5 ° is CNT diffraction maximum, and 40.2 ° is Pd diffraction maximum;
In Fig. 1, each label is:
1-is the XRD collection of illustrative plates of catalyst prepared by the present embodiment 9,
2-is the XRD collection of illustrative plates of catalyst prepared by the present embodiment 14,
3-is the XRD collection of illustrative plates of catalyst prepared by the present embodiment 15,
4-is the XRD collection of illustrative plates of catalyst prepared by the present embodiment 16,
5-is the XRD collection of illustrative plates of pure nano-carbon tube.
Fig. 2: be the transmission electron microscope picture of supported palladium/carbon nano-tube catalyst under the ultrasonic state of the present embodiment 14;
In fig. 2, scale is 50 nm;
In Fig. 2, each label is: 6-Pd particle.
Fig. 3: be supported palladium/carbon nano-tube catalyst transmission electron microscope picture under non-ultrasonic state, Pd load capacity is 5.26%;
In figure 3, scale is 100 nm, Pd load capacity is 5.66wt%;
In Fig. 3, each label is: 7-Pd particle.
Fig. 4: be the scanning electron microscope (SEM) photograph of supported palladium/carbon nano-tube catalyst under the ultrasonic state of the present embodiment 14;
In the diagram, scale is 500 nm, Pd load capacity is 5.66wt%.
Fig. 5: be pure nano-carbon tube scanning electron microscope (SEM) photograph;
In Figure 5, scale is 500 nm, is Fig. 4 control group.
detailed description of the invention:
Embodiment 1
In reaction vessel slurry bed system, be CNTs(CNT in mass ratio): water=1:45 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 20 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.28wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.25g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 20 minutes, the NaOH alkaline solution adding 15wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 40 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.28wt% of CNT, this catalyst be a kind of in carbon nano tube surface the dispersed surface having nanoparticle palladium to be formed be hair shape, for the palladium/carbon nano-tube catalyst of anthraquinone hydrogenation, the particle diameter of described nanoparticle palladium is 2 ~ 4nm.
Below provide the hydrogenation efficiency evaluation of the prepared palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation:
In flask and autoclave, get a certain amount of catalyst and join in anthraquinone working solution, hydrogenation temperature 50 ~ 53 DEG C, hydrogen flowing quantity 30 ~ 50ml/min, hydrogenation a period of time, hydride in normal temperature oxidation, oxygen flow 30 ~ 60ml/min, oxidization time 90 ~ 120min.Oxidated solution body use water extraction 3 ~ 4 times, hydrogen peroxide content in permanganimetric method titrimetry aqueous phase, calculates the catalytic efficiency of catalyst.
The catalytic activity of palladium/carbon nano-tube catalyst represents with the catalytic efficiency E of catalyst.The catalytic efficiency of catalyst is the ability that in 1 hour, unit mass palladium chtalyst hydrogenation anthraquinone working solution prepares 100% hydrogen peroxide, unit gH
2o
2(gPdh)
-1.
The size of catalytic activity represents with catalytic efficiency E, and its computational methods are as follows:
2KMnO
4+5H
2O
2+3H
2SO
4→ K
2SO
4+2MnSO
4+8H
2O
2+5O
2
E=2.5×C
KV
KMV
G/(mVw)
C in formula
k, V
kfor concentration and the volume of titration potassium permanganate, M is hydrogen peroxide molal weight, V
g/ m is the ratio that working solution volume and catalyst add quality, and V is the volume of extraction oxidation solution, and w is the mass fraction that palladium accounts for catalyst.
High dispersive palladium/carbon nano-tube catalyst catalytic efficiency at ambient pressure that the present embodiment is prepared into is 200 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 450 gH
2o
2(gPdh)
-1.
Embodiment 2
In reaction vessel slurry bed system, be CNTs(CNT in mass ratio): water=1:45 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 22 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 15 minutes, the NaOH alkaline solution adding 15wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 40 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 400 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 700 gH
2o
2(gPdh)
-1.
Embodiment 3
In reaction vessel slurry bed system, be CNTs(CNT in mass ratio): water=1:45 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 26 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 2.52wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 1.0g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 18 minutes, the NaOH alkaline solution adding 15wt% regulates the pH of palladium ion/carbon nano tube suspension to be 10 ~ 11, continue to keep machinery and ultrasonic wave to stir, be warming up to 40 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 12 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 2.52wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 410 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 720 gH
2o
2(gPdh)
-1.
Embodiment 4
In reaction vessel flask, be CNTs(CNT in mass ratio): water=1:100 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 25 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 20 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 11 ~ 13, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 450 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 850 gH
2o
2(gPdh)
-1.
Embodiment 5
In reaction vessel flask, be CNTs(CNT in mass ratio): water=1:100 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 28 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 22 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 60 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 420 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 780 gH
2o
2(gPdh)
-1.
Embodiment 6
In reaction vessel stirred tank, be CNTs(CNT in mass ratio): water=1:150 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 28 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 16 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 470 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 880 gH
2o
2(gPdh)
-1.
Embodiment 7
In reaction vessel stirred tank, be CNTs(CNT in mass ratio): water=1:100 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 20 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 25 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive glucose solution, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 430 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 720 gH
2o
2(gPdh)
-1.
Embodiment 8
In reaction vessel stirred tank, be CNTs(CNT in mass ratio): water=1:100 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 20 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 28 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive sodium formate solution, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 440 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 830 gH
2o
2(gPdh)
-1.
Embodiment 9
In reaction vessel slurry bed system, be CNTs(CNT in mass ratio): water=1:150 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 20 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 8.26wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 2.0g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 20 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 8.26wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 380 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 690gH
2o
2(gPdh)
-1.
Embodiment 10
In reaction vessel flask, be CNTs(CNT in mass ratio): water=1:100 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 28 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 26 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 40 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 410 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 730gH
2o
2(gPdh)
-1.
Embodiment 11
In slurry bed system stirred tank, be CNTs(CNT in mass ratio): water=1:45 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 20 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 20 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 420 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 760gH
2o
2(gPdh)
-1.
Embodiment 12
In stirred tank, be CNTs(CNT in mass ratio): water=1:45 adds CNT and water, it is even that ultrasonic wave is stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 30 minutes, ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 0.84wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.125g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 30 minutes, the NaOH alkaline solution adding 30wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep ultrasonic wave to stir, be warming up to 55 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 0.84wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 400 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 700 gH
2o
2(gPdh)
-1.
Embodiment 13
In flask, be CNTs(CNT in mass ratio): water=1:45 adds CNT and water, mechanical agitation is even to carbon nanotube dispersed, obtained carbon nano tube suspension, after 25 minutes, keep mechanical agitation, by Pd(nanoparticle palladium) load capacity be that the 2.52wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 1.0g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 10 minutes, the NaOH alkaline solution adding 20wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep mechanical agitation, be warming up to 45 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 2.52wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 410 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 720 gH
2o
2(gPdh)
-1.
Embodiment 14
In reaction vessel stirred tank, be CNTs(CNT in mass ratio): water=1:100 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 20 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 5.66wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 20 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 5.66wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 420 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 770gH
2o
2(gPdh)
-1.
Embodiment 15
In reaction vessel stirred tank, be CNTs(CNT in mass ratio): water=1:100 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 20 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 2.92wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 20 minutes, the NaOH alkaline solution adding 25wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 2.92wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 410 gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 780gH
2o
2(gPdh)
-1.
Embodiment 16
In reaction vessel stirred tank, be CNTs(CNT in mass ratio): water=1:100 adds CNT and water, it is even that machinery and ultrasonic wave are stirred to carbon nanotube dispersed, obtained carbon nano tube suspension, after 20 minutes, machinery and ultrasonic wave is kept to stir, by Pd(nanoparticle palladium) load capacity be that the 1.11wt% of CNT slowly drips the palladium bichloride hydrochloric acid solution that appropriate concentration is 0.50g/L in carbon nano tube suspension, obtain palladium ion/carbon nano tube suspension, after 20 minutes, the NaOH alkaline solution adding 15wt% regulates the pH of palladium ion/carbon nano tube suspension to be 9 ~ 12, continue to keep machinery and ultrasonic wave to stir, be warming up to 50 DEG C and add excessive formalin, and continuation NaOH solution regulates and keeps pH to be 10 ~ 14, until pH is substantially constant in 30min, filter, washing, 90 DEG C of vacuum drying, the load capacity obtaining Pd is the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation of the 1.11wt% of CNT.Get a certain amount of high dispersive palladium/carbon nano-tube catalyst be prepared into for anthraquinone hydrogenation evaluation, its evaluation method is with embodiment 1, and the catalytic efficiency under normal pressure is 480gH
2o
2(gPdh)
-1, under pressurization 0.3MPa, catalytic efficiency is 850gH
2o
2(gPdh)
-1.
Below, moisture, phosphoric acid is tested on the impact of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation that the present embodiment is prepared into:
1. to choose in embodiment 4 the high dispersive palladium/carbon nano-tube catalyst of system, add 0.5ml water respectively and 0.5ml phosphoric acid carries out hydrogenation evaluation before carrying out evaluating catalyst, evaluation result is as table 1:
Table 1: water, phosphoric acid are to catalysts influence tables of data
| Numbering | Catalyst type | Palladium load capacity/% | Anthraquinone working solution consumption/ml | Water/ml | Phosphoric acid/ml | Catalytic efficiency/[gH 2O 2·(gPd·h) -1] |
| 1 | Pd/ CNT | 0.84 | 70 | 0 | 0 | 850 |
| 2 | Pd/ CNT | 0.84 | 70 | 0.5 | 0 | 830 |
| 3 | Pd/ CNT | 0.84 | 70 | 0 | 0.5 | 850 |
2. conventional catalyst (Pd/ γ-Al
2o
3) control group:
Adopt Pd/ γ-Al
2o
3catalyst carries out hydrogenation evaluation, and under normal pressure, catalytic efficiency is 25 gH
2o
2(gPdh)
-1, under 0.3MPa, catalytic efficiency is 105 gH
2o
2(gPdh)
-1.
Be below each parameter lookup table in the implementation case:
Table 2: the carrying capacity table of comparisons
a
Note a: embodiment 9 is the catalyst of 50 DEG C of preparations, embodiment 1 ~ 3 is the catalyst of 40 DEG C of preparations.
Table 3: the temperature table of comparisons
b
Note b: in catalyst, Pd carrying capacity is 0.84wt%, CNTs: water=1:100, and reducing agent is formaldehyde.
Table 4: carbon nano tube suspension ratio control table
c
Note c: in catalyst, Pd carrying capacity is 0.84wt%, temperature 50 C, and reducing agent is formaldehyde.
Table 5: the different reducing agent table of comparisons
d
Note d: in catalyst, Pd carrying capacity is 0.84wt%, reduction temperature 50 DEG C, CNTs: water=1:100.
Below for observe gained from accompanying drawing:
In FIG, increase with load capacity, CNT diffraction maximum weakens, and Pd has good distribution in carbon nano tube surface.
In fig. 2, Pd particle is more homogeneous nano particle, and particle diameter is 2 ~ 4nm.
In figure 3, the catalyst cupport particle of not ultrasonic process preparation is uneven.
In the diagram, the metallic particles of carbon nano tube surface load can be found out.
In Figure 5, carbon nano tube surface is comparatively smooth.
Claims (10)
1. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation: it is characterized in that: comprise the steps:
A. in reaction vessel, add CNT and water for 1:45 ~ 150 in mass ratio, be stirred to carbon nanotube dispersed even, obtained carbon nano tube suspension;
B. keep stirring, the 0.28wt% ~ 1.11wt% being CNT by the load capacity of nanoparticle palladium in the carbon nano tube suspension obtained in steps A slowly drips the palladium bichloride hydrochloric acid solution that concentration is 0.125 ~ 2g/L, obtains palladium ion/carbon nano tube suspension;
C. pH=9 ~ 12 that alkaline solution regulates palladium ion/carbon nano tube suspension are dripped in stepb;
D.
keep stirring, raised temperature to 40 ~ 60 DEG C also add excessive reducing agent, regulate and keep pH=9 ~ 14 to carry out reduction reaction;
E. filter, wash and drying, obtain the high dispersive palladium/carbon nano-tube catalyst for anthraquinone hydrogenation.
2. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 1, is characterized in that: described stirring refers to and adopts mechanical agitation or adopt ultrasonic wave to stir or adopt machinery and ultrasonic wave jointly to stir.
3. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 2, is characterized in that: the mixing time in described steps A is 20 ~ 30 minutes.
4. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 1, is characterized in that: the interval time between step B and step C is 10 ~ 30 minutes.
5. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 1, is characterized in that: alkaline solution used in step C is the NaOH solution of 15 ~ 30wt%.
6. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 1, is characterized in that: reducing agent used is in step D formaldehyde, glucose or sodium formate.
7. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 1, is characterized in that: the reduction reaction terminal described in step D is that the pH of palladium ion/carbon nano tube suspension no longer changes.
8. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 1 to the arbitrary claim of claim 7, is characterized in that: described reaction vessel is slurry bed system or flask or stirred tank.
9. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 8, it is characterized in that: described high dispersive palladium/carbon nano-tube catalyst be a kind of in carbon nano tube surface the dispersed surface having nanoparticle palladium to be formed be hair shape, be mainly used in the palladium/carbon nano-tube catalyst of anthraquinone hydrogenation, the load capacity of described nanoparticle palladium is the 0.28wt% ~ 1.11wt% of CNT.
10. the preparation method of the palladium/carbon nano-tube catalyst of the high dispersive for anthraquinone hydrogenation according to claim 9, is characterized in that: the particle diameter of described nanoparticle palladium is 2 ~ 4nm.
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| CN105268433A (en) * | 2014-06-13 | 2016-01-27 | 中国科学院大连化学物理研究所 | Highly-dispersed catalyst for hydrogen peroxide synthesis and preparation method thereof |
| CN104401944A (en) * | 2014-10-29 | 2015-03-11 | 广西田东达盛化工科技有限公司 | Preparation process of high-purity hydrogen peroxide |
| CN104475093B (en) * | 2014-11-26 | 2016-08-24 | 中国石油大学(北京) | The carbon nano tube compound material of Pd/PdO nanometer particle load and preparation method thereof and application |
| CN106540689A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of CNT carried palladium catalyst and its preparation method and application |
| CN106693958B (en) * | 2015-11-12 | 2019-04-09 | 中触媒新材料股份有限公司 | A kind of hydrogenating alkyl anthraquinone catalyst and preparation method thereof |
| CN106390999A (en) * | 2016-09-18 | 2017-02-15 | 中国天辰工程有限公司 | Novel anthraquinone hydrogenation slurry bed catalyst, and preparation method thereof |
| CN106732563B (en) * | 2017-01-24 | 2019-11-01 | 厦门大学 | A kind of preparation method of palladium carbon catalyst |
| CN107081149A (en) * | 2017-05-16 | 2017-08-22 | 武汉理工大学 | A kind of anthraquinone simplification preparation method for preparing hydrogen peroxide low energy consumption hydrogenation catalyst |
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