CN105126840A - Efficiently supported palladium catalyst for hydrogenation process of H2O2 production with anthraquinone method and preparation method of efficiently supported palladium catalyst - Google Patents
Efficiently supported palladium catalyst for hydrogenation process of H2O2 production with anthraquinone method and preparation method of efficiently supported palladium catalyst Download PDFInfo
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Abstract
The invention discloses an efficiently supported palladium catalyst for a hydrogenation process of H2O2 production with an anthraquinone method and a preparation method of the efficiently supported palladium catalyst. According to the supported catalyst, gamma-Al2O3 is taken as a support, a main active component is Pd-, and the capacity of the main active component is 0.1%-1.0% in percentage by mass; assistants are Si- and La-, and the capacity of Si- and the supporting capacity of La- are 0.1%-0.5% in percentage by mass and 1.7%-6.0% in percentage by mass respectively. The preparation method of the supported catalyst mainly comprises steps as follows: equivalent-volume impregnation of gamma-Al2O3 with a sodium silicate solution, equivalent-volume impregnation of a Si- modified gamma-Al2O3 based composite support with a lanthanum nitrate hexahydrate solution, equivalent-volume impregnation of a composite support Si-La/gamma-Al2O3 with a palladium chloride solution and the like. The prepared supported palladium catalyst Pd-La-Si/gamma-Al2O3 has the characteristics of high activity and high selectivity, the grain size of Pd- in the catalyst commonly ranges from 5 nm to 10 nm, the hydrogenation efficiency can be up to 11.05-12.96 g (H2O2)/L working solution, and the selectivity can be higher than 97.9%.
Description
Technical field
The present invention relates to a kind of anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst and preparation method thereof.
Background technology
H
2o
2be a kind of green chemical products, be widely used in the industries such as chemical industry, papermaking, environmental protection, electronics, food, medicine, weaving, mining industry and agricultural residue processing.H
2o
2production method a lot, wherein anthraquinone is produce H both at home and abroad
2o
2main method.Anthraquinone hydrogenation catalytic process is anthraquinone core, and wherein, load type palladium catalyst is the most also most popular catalyst at present, wherein with Pd/ γ-Al
2o
3catalyst application is the most extensive, and in its catalytic activity, selective and catalyst, the height of precious metals pd-content just becomes restriction anthraquinone legal system H
2o
2the key factor of hydrogenation efficiency and production cost.But existing Pd/ γ-Al
2o
3in catalyst, the content of Pd-is generally higher, and part Pd-can not play catalytic action because containing well in carrier inside, also has that activity is not high, perishable, aging, a problem such as inactivation and active component come off.Therefore, how in reduction load type palladium catalyst, to make it have higher activity and selectivity while Pd-load capacity, be Pd/ γ-Al
2o
3the important directions of catalyst development.
To fixed bed anthraquinone production H
2o
2with load type palladium catalyst, in the process of carrier loaded active component, add suitable auxiliary agent and can reach raising catalyst activity and improve its optionally object.Such as, patent CN103071487A discloses a kind of anthraquinone fixed bed hydrogenation palladium catalyst and preparation method thereof.Catalyst carrier is the Woelm Alumina containing alkali metal or alkaline-earth metal and transition metal oxide or rare-earth oxide, aluminium source be in aluminum sulfate and sodium metaaluminate and obtained powder with boehmite in mass ratio for 70-90:30-10 mixes the colloidal sol obtained, aluminium oxide crystal formation be γ-, δ-, θ-and α-Al
2o
3in one or more; The transition metal added is at least one in Cr-, Zn-, Mn-, Cu-, Fe-, Co-, Ni-, Zr-, Nb-and Mo-, and the rare earth metal of interpolation is at least one in La-, Ce-, Sm-, Pr-and Nd-; In carrier, the mass ratio of aluminium oxide and transition metal or rare-earth oxide is 100:0.5-10, and the hydrogenation efficiency of this catalyst in fixed bed hydrogenation reactor is 7.76 ~ 10.31g (H
2o
2)/L working solution.Patent CN102389799A discloses a kind of employing fixed bed anthraquinone production H
2o
2palladium catalyst and manufacture method, the aluminium source of alumina support changes aluminum sulfate into and mixes obtained colloidal sol with the powder obtained with obtained powder and aluminum sulfate and ammonia neutralization in sodium aluminate with weight ratio 1:0.1 ~ 1.0, additive alkali metal or alkaline-earth metal and transition metal salt by 1:1 concentration mixed dissolution and be carried on after on carrier, the more main active component Pd-of load.Patent CN1435277A discloses a kind of for anthraquinone production H
2o
2alumina load type palladium catalyst and preparation method thereof, this catalyst is to apply rare earth oxide in advance and through the aluminium oxide of 900-1000 DEG C of high-temperature calcination for carrier, rare earth oxide coated weight is the load capacity of 0.1-15%, Pd-is 0.15-0.25%.In this catalyst, the load capacity of Pd-decreases, and its hydrogenation efficiency in micro fixed-bed reactor is 10-13g (H
2o
2)/L working solution.
CN1398775A discloses anthraquinone preparation H in a kind of trickle bed reactor
2o
2hydrogenation catalyst and preparation, this catalyst adopts the method preparation of infusion process wet reducing, it is characterized in that with Al
2o
3or containing 80%TiO
2al
2o
3-TiO
2composite oxides are carrier, and with Pt-, Pd-for altogether active component, with at least one in La-, Ce-, Pr-, Sm-for auxiliary agent, the atomic ratio between its carrier and active component and thulium auxiliary agent is: Pt and Pd: Al and Ti=1.7 × 10
-4~ 1.7 × 10
-1, Pt: Pd=1.0 ~ 30.0, Pt, Pd: auxiliary element=0.05 ~ 3.0, hydrogenation efficiency is 9-11g (H
2o
2)/L working solution.The deficiency of this catalyst contains than Pd Pt element costly.
Patent CN1990100A discloses a kind of based on infusion process and for the anthraquinone hydrogenation catalyst of tubular reactor, this catalyst is made up of matrix, carrier and active component, wherein, matrix is cordierite or the foamed alumina of the regular parallel pore passage structure with both ends open; Carrier is 5 ~ 35% of matrix weight, for be coated in matrix surface gama-alumina, be oxidized and be selected from cerium oxide, lanthana and protactinium oxide one or more; Active constituent loading is on carrier surface, be made up of the mixture of component A or component A and B component, component A is Pd-and/or Pt-, and content is 0.5 ~ 5% of carrier, B component is one or more in Ti-, Zr-, Hf-, Mn-, Co-, Ce-and La-, and content is 0 ~ 1% of carrier.This catalyst application reacts in anthraquinone hydrogenation, and conversion ratio is about 70 ~ 90%.Patent CN101966454A discloses a kind of for anthraquinone legal system H
2o
2catalysts and its preparation method, this patent by Metal Palladium colloidal sol and rare-earth metal nitrate solution are added drop-wise in the slurries of boehmite, and through stirring reaction, rotary evaporation, except desolventizing, is dried, grinding, roasting, the loading type Pd-series catalysts of obtained alumina load.In embodiment catalyst, the content of Pd-is about 0.295 ~ 1.007wt%, the content of rare-earth oxide (La-, Sm-and Ce-etc.) is about 0 ~ 2.5wt%, porous carbon is 0.01 ~ 0.05wt%, all the other are carrier alundum, but the average grain diameter of higher, the Pd-metallic particles of the content of Pd-comparatively large (being about 10nm) in this catalyst, hydrogenation conversion ratio is only 82 ~ 96%, and does not mention the selective of object product.Patent CN1347757A discloses a kind of hydrogenating alkyl anthraquinone loaded platinum catalyst, working solution and H in stainless steel reactor
2from up to down plug flow, hydrogenation efficiency is 7.5 ~ 12.0g (H
2o
2)/L working solution.This catalyst is by γ-Al
2o
3the active component Pt-of carrier, 0.2 ~ 0.4wt%, the auxiliary agent K of 0.3 ~ 1.2wt%
2o or Cs
2o or MgO or BaO or La
2o
3or CeO
2composition, its predecessor can be nitrate, acetate or chloride.
But so far, also do not use the report of the support type anthraquinone hydrogenation catalyst of Si-modification.
Summary of the invention
The technical problem to be solved in the present invention is: provide that a kind of active component Pd-consumption is few, high, the selective good and stability of hydrogenation conversion efficiency is high for anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst and preparation method thereof, to improve its decentralization at catalyst surface while precious metals pd-load capacity reducing, makes the particle diameter of Pd-particle be decreased to 5 ~ 10nm.
The present invention solves its technical problem and adopts following technical scheme:
Anthraquinone production H provided by the invention
2o
2hydrogenation process high efficiency load type palladium catalyst, is characterized in that this catalyst is made up of main active component, auxiliary agent and carrier, and described main active component is Pd-, and its load capacity is 0.1 ~ 1.0%; Auxiliary agent is Si-and La-, and its load capacity is respectively 0.1 ~ 0.5% and 1.7 ~ 6.0%; Carrier is γ-Al
2o
3.
Above-mentioned anthraquinone production H provided by the invention
2o
2hydrogenation process high efficiency load type palladium catalyst, its preparation method adopts following steps:
First, take the dry activated alumina fully of 1.0g, at 60 DEG C, adopt sodium silicate solution incipient impregnation 2h, the suspension obtained is after suction filtration separation, distilled water washing leaching cake to weakly acidic pH, in 100 ~ 160 DEG C by filtration cakes torrefaction 2 ~ 6h, obtain the γ-Al of Si-modification
2o
3base complex carrier.Then, at 60 DEG C, adopt lanthanum nitrate hexahydrate solution incipient impregnation 2h, La-is loaded on the complex carrier of above-mentioned Si-modification; The suspension obtained through suction filtration be separated after, with distilled water washing leaching cake to weakly acidic pH; Above-mentioned filter cake after roasting 3-5h, is obtained complex carrier Si-La/ γ-Al successively at 100 ~ 160 DEG C of drying 2 ~ 6h, 400-600 DEG C
2o
3.
Finally, the above-mentioned product of roasting 2h of palladium chloride solution incipient impregnation is adopted at 60 DEG C, the above-mentioned compound of the excessive dipping of NaOH solution of further employing 0.1M, the suspension obtained is after suction filtration is separated, with distilled water washing leaching cake to weakly acidic pH, by filter cake successively at 100 ~ 160 DEG C dry 2 ~ 6h, at 400 ~ 600 DEG C after roasting 3 ~ 4h, obtained described high efficiency load type palladium catalyst.
In technique scheme, in prepared catalyst, the content of active component Pd-is 0.1 ~ 1wt%, and the content of adjuvant component Si-is 0.1 ~ 0.5wt%, the content of La-is 1.7 ~ 6.0wt%.
In technique scheme, palladium chloride solution is formed after the HCl solubilize palladium bichloride of 2 ~ 4 by pH value.
In technique scheme, in Kaolinite Preparation of Catalyst process, adopt the condition of the excessive dipping of NaOH solution as follows: with the compound 1h after this solution impregnation load P d-of 4ml, 0.1M at 60 DEG C.
In technique scheme, sodium metasilicate and lanthanum nitrate hexahydrate substep incipient impregnation is adopted to contribute to auxiliary agent Si-and La-at γ-Al
2o
3dispersion in carrier, wherein, auxiliary agent La-not only effectively can improve the activity of catalyst, also has good peptizaiton to active component Pd-.
In technique scheme, distilled water suction filtration, washing sodium metasilicate and lanthanum nitrate hexahydrate impregnation product is adopted to be the loads being conducive to active component Pd-in follow-up dipping process to neutral object.
In technique scheme, the object adopting palladium bichloride to make Pd-predecessor be its load capacity lower time, be conducive to Pd in the carrier dispersed and the particle diameter of catalyst is more even.In palladium chloride solution dipping process with hydrochloric acid solution regulate its pH value 2 ~ 4 object be that control Pd layer thickness is thinner, improve it at the decentralization of carrier surface and reduce the size of Pd particle.
In technique scheme, the object adopting the excessive dipping of 4mlNaOH solution makes Pd ion fully be hydrolyzed and be deposited to carrier surface.
Catalyst prepared by the present invention is 80 ~ 320 orders, comparatively be adapted at carrying out hydrogenation reaction in suspension bed (slurry bed system) reactor, less particle is beneficial to suspension, particle is suspended in reaction liquid uniformly, the prepared catalyst obtained without shaping, can carry out anthraquinone atmospheric hydrogenation in the liquid phase.
The technique of Kaolinite Preparation of Catalyst of the present invention is simple, mild condition, has the potentiality of industrial applications.
Accompanying drawing explanation
Fig. 1 is γ-Al
2o
3the SEM picture of carrier.
Fig. 2 is Pd/ γ-Al
2o
3the SEM picture of catalyst.
Fig. 3 is Pd-La-Si/ γ-Al
2o
3the SEM picture of catalyst.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, and these embodiments are only the descriptions to better embodiment of the present invention, but are not limited to described content below.
Embodiment 1:
First, the γ-Al that 1.0g is fully dry is taken
2o
3to in the beaker of 50ml.Then, take 0.0103g sodium metasilicate, adopt equi-volume impregnating to flood 2h at 60 DEG C, Si-is loaded on activated alumina; The suspension obtained, after suction filtration separation, distilled water washing leaching cake to weakly acidic pH, by filter cake dry 6h at 100 DEG C, obtains the γ-Al of Si-modification
2o
3base complex carrier.
Then, take 0.1511g lanthanum nitrate hexahydrate, adopt equi-volume impregnating to flood 2h at 60 DEG C, La-is loaded to the γ-Al of above-mentioned Si-modification
2o
3on base complex carrier; The suspension obtained is separated through suction filtration, after distilled water washing leaching cake to weakly acidic pH, by filter cake successively at 160 DEG C dry 2h, at 400 DEG C after roasting 5h, obtain complex carrier Si-La/ γ-Al
2o
3.
Finally, take 0.0017g palladium bichloride, and dissolved with the HCl solution of pH=2, form palladium chloride solution, adopt equi-volume impregnating, at 60 DEG C, above-mentioned complex carrier is flooded 2h, Pd-is loaded to Si-La/ γ-Al
2o
3on; Further employing excess solution impregnation method, above-mentioned compound 1h is flooded by the NaOH solution of 0.1M at 60 DEG C, the suspension obtained is after suction filtration is separated, with distilled water washing leaching cake to weakly acidic pH, by the filter cake that obtains successively at 120 DEG C dry 4h, at 600 DEG C after roasting 3h, i.e. obtained anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst 0.1%Pd-6%La-0.1%Si/ γ-Al
2o
3.
The test of described high efficiency load type palladium catalyst hydrogenation efficiency: the hydrogenation efficiency recording this catalyst in paste state bed reactor is 11.73g (H
2o
2)/L working solution, selective be 100%.
Embodiment 2:
First, the γ-Al that 1.0g is fully dry is taken
2o
3to in the beaker of 50ml.Then, take 0.0114g sodium metasilicate, adopt equi-volume impregnating to flood 2h at 60 DEG C, Si-is loaded on activated alumina; Filter cake, after suction filtration separation, distilled water washing leaching cake to weakly acidic pH, after dry 2h, is obtained the γ-Al of Si-modification by the suspension obtained at 160 DEG C
2o
3base complex carrier.
Then, take 0.0831g lanthanum nitrate hexahydrate, adopt equi-volume impregnating to flood 2h at 60 DEG C, La-is loaded to the γ-Al of above-mentioned Si-modification
2o
3on base complex carrier; The suspension system obtained, after suction filtration is separated, is neutral with distilled water washing, suction filtration to filter cake; By above-mentioned neutral filter cake successively at 160 DEG C dry 2h, at 600 DEG C, after roasting 3h, obtain complex carrier Si-La/ γ-Al
2o
3.
Finally, take 0.0050g palladium bichloride, and dissolved with the HCl solution of pH=3, form palladium chloride solution, adopt equi-volume impregnating, at 60 DEG C, above-mentioned complex carrier is flooded 2h, Pd-is loaded to Si-La/ γ-Al
2o
3on; Further employing excess solution impregnation method, above-mentioned compound 1h is flooded by the NaOH solution of 0.1M at 60 DEG C, the suspension obtained is after suction filtration is separated, with distilled water washing leaching cake to weakly acidic pH, by the filter cake that obtains successively at 160 DEG C dry 2h, at 500 DEG C after roasting 4h, i.e. obtained anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst 0.3%Pd-3.42%La-0.11%Si/ γ-Al
2o
3.
The test of described high efficiency load type palladium catalyst hydrogenation efficiency: the hydrogenation efficiency recording this catalyst in paste state bed reactor is 12.58g (H
2o
2)/L working solution, selective be 97.9%.
Embodiment 3:
First, the γ-Al that 1.0g is fully dry is taken
2o
3to in the beaker of 50ml.Then, take 0.0344g sodium metasilicate, adopt equi-volume impregnating to flood 2h at 60 DEG C, Si-is loaded on activated alumina; The suspension obtained after suction filtration is separated, then is neutral with distilled water washing, suction filtration to filter cake; Above-mentioned filter cake after dry 4h, obtains the γ-Al of Si-modification at 120 DEG C
2o
3base complex carrier.
Then, take 0.0617g lanthanum nitrate hexahydrate, adopt equi-volume impregnating to flood 2h at 60 DEG C, La-is loaded to the γ-Al of above-mentioned Si-modification
2o
3on base complex carrier; The suspension system obtained, after suction filtration is separated, is neutral with distilled water washing, suction filtration to filter cake; By above-mentioned neutral filter cake successively at 120 DEG C dry 4h, at 500 DEG C, after roasting 4h, obtain complex carrier Si-La/ γ-Al
2o
3.
Finally, take 0.0050g palladium bichloride, and dissolved with the HCl solution of pH=3, form palladium chloride solution, adopt equi-volume impregnating, at 60 DEG C, above-mentioned complex carrier is flooded 2h, Pd-is loaded to Si-La/ γ-Al
2o
3on; Further employing excess solution impregnation method, above-mentioned compound 1h is flooded by the NaOH solution of 0.1M at 60 DEG C, the suspension obtained is after suction filtration is separated, with distilled water washing leaching cake to weakly acidic pH, by the filter cake that obtains successively at 120 DEG C dry 4h, at 500 DEG C after roasting 4h, i.e. obtained anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst 0.3%Pd-2.56%La-0.34%Si/ γ-Al
2o
3.
The test of described high efficiency load type palladium catalyst hydrogenation efficiency: the hydrogenation efficiency recording this catalyst in paste state bed reactor is 12.96g (H
2o
2)/L working solution, selective be 100%.
Embodiment 4:
First, the γ-Al that 1.0g is fully dry is taken
2o
3to in the beaker of 50ml.Then, take 0.0228g sodium metasilicate, adopt equi-volume impregnating to flood 2h at 60 DEG C, Si-is loaded on activated alumina; The suspension obtained after suction filtration is separated, then is neutral with distilled water washing, suction filtration to filter cake; Above-mentioned filter cake after dry 2h, obtains the γ-Al of Si-modification at 160 DEG C
2o
3base complex carrier.
Then, take 0.1050g lanthanum nitrate hexahydrate, adopt equi-volume impregnating to flood 2h at 60 DEG C, La-is loaded to the γ-Al of above-mentioned Si-modification
2o
3on base complex carrier; The suspension system obtained, after suction filtration is separated, is neutral with distilled water washing, suction filtration to filter cake; By above-mentioned neutral filter cake successively at 160 DEG C dry 2h, at 500 DEG C, after roasting 4h, obtain complex carrier Si-La/ γ-Al
2o
3.
Finally, take 0.0050g palladium bichloride, and dissolved with the HCl solution of pH=3.5, form palladium chloride solution, adopt equi-volume impregnating, at 60 DEG C, above-mentioned complex carrier is flooded 2h, Pd-is loaded to Si-La/ γ-Al
2o
3on; Further employing excess solution impregnation method, above-mentioned compound 1h is flooded by the NaOH solution of 0.1M at 60 DEG C, the suspension obtained is after suction filtration is separated, with distilled water washing leaching cake to weakly acidic pH, by the filter cake that obtains successively at 120 DEG C dry 4h, at 500 DEG C after roasting 4h, i.e. obtained anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst 0.3%Pd-1.7%La-0.22%Si/ γ-Al
2o
3.
The test of described high efficiency load type palladium catalyst hydrogenation efficiency: the hydrogenation efficiency recording this catalyst in paste state bed reactor is 12.58g (H
2o
2)/L working solution, selective be 100%.
Embodiment 5:
First, the γ-Al that 1.0g is fully dry is taken
2o
3to in the beaker of 50ml.Then, take 0.0403g sodium metasilicate, adopt equi-volume impregnating to flood 2h at 60 DEG C, Si-is loaded on activated alumina; The suspension obtained after suction filtration is separated, then is neutral with distilled water washing, suction filtration to filter cake; Above-mentioned filter cake after dry 6h, obtains the γ-Al of Si-modification at 100 DEG C
2o
3base complex carrier.
Then, take 0.0831g lanthanum nitrate hexahydrate, adopt equi-volume impregnating to flood 2h at 60 DEG C, La-is loaded to the γ-Al of above-mentioned Si-modification
2o
3on base complex carrier; The suspension system obtained, after suction filtration is separated, is neutral with distilled water washing, suction filtration to filter cake; By above-mentioned neutral filter cake successively at 100 DEG C dry 6h, at 500 DEG C, after roasting 4h, obtain complex carrier Si-La/ γ-Al
2o
3.
Finally, take 0.0050g palladium bichloride, and dissolved with the HCl solution of pH=3.5, form palladium chloride solution, adopt equi-volume impregnating, at 60 DEG C, above-mentioned complex carrier is flooded 2h, Pd-is loaded to Si-La/ γ-Al
2o
3on; Further employing excess solution impregnation method, above-mentioned compound 1h is flooded by the NaOH solution of 0.1M at 60 DEG C, the suspension obtained is after suction filtration is separated, with distilled water washing leaching cake to weakly acidic pH, by the filter cake that obtains successively at 100 DEG C dry 6h, at 600 DEG C after roasting 3h, i.e. obtained anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst 0.3%Pd-3.42%La-0.4%Si/ γ-Al
2o
3.
The test of described high efficiency load type palladium catalyst hydrogenation efficiency: the hydrogenation efficiency recording this catalyst in paste state bed reactor is 11.48g (H
2o
2)/L working solution, selective be 98.3%.
Embodiment 6:
First, the γ-Al that 1.0g is fully dry is taken
2o
3to in the beaker of 50ml.Then, take 0.0524g sodium metasilicate, adopt equi-volume impregnating to flood 2h at 60 DEG C, Si-is loaded on activated alumina; The suspension obtained after suction filtration is separated, then is neutral with distilled water washing, suction filtration to filter cake; Above-mentioned filter cake after dry 4h, obtains the γ-Al of Si-modification at 120 DEG C
2o
3base complex carrier.
Then, take 0.0480g lanthanum nitrate hexahydrate, adopt equi-volume impregnating to flood 2h at 60 DEG C, La-is loaded to the γ-Al of above-mentioned Si-modification
2o
3on base complex carrier; The suspension system obtained, after suction filtration is separated, is neutral with distilled water washing, suction filtration to filter cake; By above-mentioned neutral filter cake successively at 120 DEG C dry 4h, at 600 DEG C, after roasting 3h, obtain complex carrier Si-La/ γ-Al
2o
3.
Finally, take 0.0169g palladium bichloride, and dissolved with the HCl solution of pH=4, form palladium chloride solution, adopt equi-volume impregnating, at 60 DEG C, above-mentioned complex carrier is flooded 2h, Pd-is loaded to Si-La/ γ-Al
2o
3on; Further employing excess solution impregnation method, above-mentioned compound 1h is flooded by the NaOH solution of 0.1M at 60 DEG C, the suspension obtained is after suction filtration is separated, with distilled water washing leaching cake to weakly acidic pH, by the filter cake that obtains successively at 120 DEG C dry 4h, at 400 DEG C after roasting 5h, i.e. obtained anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst 1%Pd-2%La-0.5%Si/ γ-Al
2o
3.
The test of described high efficiency load type palladium catalyst hydrogenation efficiency: the hydrogenation efficiency recording this catalyst in paste state bed reactor is 11.05g (H
2o
2)/L working solution, selective be 98.7%.
Above-mentioned catalyst adopts miniature paste state bed reactor to evaluate, and reaction temperature is 60 DEG C, and loaded catalyst is 0.8g, uses H in the reactor before active testing
2reducing catalyst 1h at 60 DEG C.This experiment is industrial working solution with working solution, and its composition is: the content of effective anthraquinone 2-EAQ (EAQ) is 11.196g/L, and the content of tetrahydrochysene-2-EAQ (THEAQ) is 82.414g/L, and the consumption of working solution is 40ml.
The activity of above-mentioned catalyst represents with catalytic efficiency B, 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
(anthraquinone working solution of a certain amount of catalyst hydrogenation unit volume prepares 100%H to hydrogenation efficiency B
2o
2ability, g/L): B=17 × 5MV
1/ V
2
In formula, M is KMnO
4the concentration (mol/L) of solution, V
1for KMnO
4the consumption (ml) of solution, V
2for the volume (ml) of oxidation solution.
The selective size of above-mentioned catalyst represents with catalytic selectivity E, and its computational methods are as follows:
Hydrogenation selectivity (reacting the ratio of effective active anthraquinone in the working solution of front and back): E=n
1/ n
2
In formula, n
1for reacting the mole (mol) of rear effective active anthraquinone, n
2for reacting the mole (mol) of the effective active anthraquinone in front working solution.
γ-Al used when Fig. 1 is the application's Kaolinite Preparation of Catalyst
2o
3the SEM picture of carrier, Fig. 2 is typical Pd/ γ-Al
2o
3the SEM picture of catalyst, Fig. 3 is typical Pd-La-Si/ γ-Al
2o
3the SEM picture of catalyst, wherein, the point that in Fig. 2 and Fig. 3, white is bright represents palladium particle.As can be seen from the figure, with Pd/ γ-Al in Fig. 2 of only load P d-
2o
3the SEM picture of catalyst is compared, in Fig. 3 the particle diameter of palladium particle diminish and disperse very even, highlight active sites fully, be conducive to the activity and selectivity improving its catalytic reaction.
Embodiment 7:
Anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst, it is made up of main active component, auxiliary agent and carrier, and described main active component is Pd-, and its load capacity is 0.1 ~ 1.0%; Auxiliary agent is Si-and La-, and its load capacity is respectively 0.1 ~ 0.5% and 1.7 ~ 6.0%; Carrier is γ-Al
2o
3.
Claims (4)
1. an anthraquinone production H
2o
2hydrogenation process high efficiency load type palladium catalyst, is characterized in that this catalyst is made up of main active component, auxiliary agent and carrier, and described main active component is Pd-, and its load capacity is 0.1 ~ 1.0%; Auxiliary agent is Si-and La-, and its load capacity is respectively 0.1 ~ 0.5% and 1.7 ~ 6.0%; Carrier is γ-Al
2o
3.
2. anthraquinone production H described in claim 1
2o
2the hydrogenation process preparation method of high efficiency load type palladium catalyst, is characterized in that this preparation method implements according to the following steps:
First, the γ-Al that 1.0g is fully dry is taken
2o
3, at 60 DEG C, adopt sodium silicate solution incipient impregnation 2h, the suspension obtained, after suction filtration separation, distilled water washing leaching cake to weakly acidic pH, by above-mentioned filter cake in 100 ~ 160 DEG C of drying 2 ~ 6h, obtains the γ-Al of Si-modification
2o
3base complex carrier;
Then, at 60 DEG C, adopt lanthanum nitrate hexahydrate solution incipient impregnation 2h, La-is loaded on the complex carrier of above-mentioned Si-modification; The suspension obtained through suction filtration be separated after, with distilled water washing leaching cake to weakly acidic pH; Above-mentioned filter cake after roasting 3-5h, is obtained complex carrier Si-La/ γ-Al successively at 100 ~ 160 DEG C of drying 2 ~ 6h, 400-600 DEG C
2o
3;
Finally, the complex carrier 2h after the above-mentioned roasting of a certain amount of palladium chloride solution incipient impregnation is adopted at 60 DEG C, the excessive NaOH solution of further employing floods above-mentioned compound, the suspension obtained is after suction filtration is separated, with distilled water washing leaching cake to weakly acidic pH, by the filter cake that obtains successively at 100 ~ 160 DEG C dry 2 ~ 6h, at 400 ~ 600 DEG C after roasting 3 ~ 4h, obtained described high efficiency load type palladium catalyst.
3. anthraquinone production H according to claim 2
2o
2the hydrogenation process preparation method of high efficiency load type palladium catalyst, is characterized in that described palladium chloride solution is formed after the HCl solubilize palladium bichloride of 2 ~ 4 by pH value.
4. anthraquinone production H according to claim 2
2o
2the hydrogenation process preparation method of high efficiency load type palladium catalyst, is characterized in that adopting the condition of the excessive dipping of NaOH solution as follows: with the compound 1h after this solution impregnation load P d-of 4ml, 0.1M at 60 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391093A (en) * | 2016-08-29 | 2017-02-15 | 武汉理工大学 | Preparation method of auxiliary agent bulk-phase-distributed Pd-Zn-Ba/SBA-15 catalyst |
| CN106629797A (en) * | 2016-10-25 | 2017-05-10 | 武汉理工大学 | A double-hydrolysis reaction preparing method for texture-property-controllable gamma-aluminum oxide |
| CN108114666A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | The grading method of catalyst of anthraquinone hydrogenation |
| CN109908914A (en) * | 2019-03-13 | 2019-06-21 | 武汉理工大学 | Pd-Mg/Ni/ γ-the Al that auxiliary agent body is mutually distributed2O3Catalyst carrier microballoon and its preparation method and application |
| CN109939678A (en) * | 2019-02-14 | 2019-06-28 | 北京氦舶科技有限责任公司 | A kind of monatomic palladium catalyst and its preparation method and application |
| CN110479254A (en) * | 2019-09-12 | 2019-11-22 | 中触媒新材料股份有限公司 | A kind of method for preparing catalyst of anthraquinone hydrogenation |
| CN112717923A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof |
| CN115779899A (en) * | 2022-09-29 | 2023-03-14 | 福建省福大百阳化工科技有限公司 | Palladium-alumina catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101032699A (en) * | 2006-03-10 | 2007-09-12 | 中国石油化工股份有限公司 | Catalyst support added with hydrogen, peroxide catalyst produced by anthraquinone method and the producing process |
-
2015
- 2015-09-18 CN CN201510598323.XA patent/CN105126840A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101032699A (en) * | 2006-03-10 | 2007-09-12 | 中国石油化工股份有限公司 | Catalyst support added with hydrogen, peroxide catalyst produced by anthraquinone method and the producing process |
Non-Patent Citations (4)
| Title |
|---|
| A.DRELINKIEWICZ: "Hydrogenation of 2-ethylanthraquinone on alumina-supported palladium catalysts The effect of support modification with Na2SiO3", 《APPLIED CATALYSIS A: GENERAL》 * |
| A.DRELINKIEWICZ: "Hydrogenation of 2-ethylanthraquinone over Pd/SiO2 and Pd/Al2O3 in the fixed-bed reactor. The effect of the type of support", 《CATALYSIS LETTERS》 * |
| QING LI: "Palladium Nanoparticles Supported on γ-Al2O3 for Hydrogenation of 2-Tertiary Butyl Anthraquinone to produce H2O2", 《JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY》 * |
| 王榕: "稀土金属氧化物对Pd/δ,θ-Al2O3催化蒽醌制H2O2性能的影响", 《催化学报》 * |
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| CN108114666A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | The grading method of catalyst of anthraquinone hydrogenation |
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| CN109908914A (en) * | 2019-03-13 | 2019-06-21 | 武汉理工大学 | Pd-Mg/Ni/ γ-the Al that auxiliary agent body is mutually distributed2O3Catalyst carrier microballoon and its preparation method and application |
| CN109908914B (en) * | 2019-03-13 | 2022-09-30 | 武汉理工大学 | Pd-Mg/Ni/gamma-Al with bulk phase distribution of assistant 2 O 3 Catalyst carrier microsphere and preparation method and application thereof |
| CN110479254A (en) * | 2019-09-12 | 2019-11-22 | 中触媒新材料股份有限公司 | A kind of method for preparing catalyst of anthraquinone hydrogenation |
| CN112717923A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof |
| CN112717923B (en) * | 2019-10-28 | 2024-05-31 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof |
| CN115779899A (en) * | 2022-09-29 | 2023-03-14 | 福建省福大百阳化工科技有限公司 | Palladium-alumina catalyst and preparation method thereof |
| CN115779899B (en) * | 2022-09-29 | 2024-05-24 | 福建省福大百阳化工科技有限公司 | Palladium-aluminum oxide catalyst and preparation method thereof |
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