CN103706356A - Preparation method of eggshell type anthraquinone hydrogenation fixed bed catalyst - Google Patents
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Abstract
The invention relates to a preparation method of an eggshell type anthraquinone hydrogenation fixed bed catalyst, wherein the eggshell type anthraquinone hydrogenation fixed bed catalyst is prepared from a spherical Al2O3 carrier through the steps of pre-drying processing, medium temperature soaking, desalted water washing, drying, activation calcination and the like. The preparation method has the beneficial effects that the preparation process of the catalyst is simple, the production cost is low, the hydrogenation efficiency is high, the selectivity is good, the hydrogenation efficiency is greater than 9 g/L, and the selectivity is grater than 99.5%; active metal palladium of the catalyst is tightly attached to the outer surface of the catalyst and is distributed in an eggshell type, and the thickness of a soaking layer is 50-80 microns and is beneficial to efficient utilization of precious metal palladium. The working procedure of washing is introduced in the preparation process of the catalyst, and the washing process is quantified.
Description
Technical field
The invention belongs to Catalyst Production technical field, relate in particular to a kind of preparation method of eggshell type anthraquinone hydrogenation fixed bde catalyst.
Background technology
Hydrogen peroxide is the aqueous solution of hydrogen peroxide, due to its free of contamination feature in use, therefore be called as the most clean oxidant.Hydrogen peroxide is mainly used to prepare the products such as bleaching agent, disinfectant, deoxidier, polymerization initiator and crosslinking agent at present, is widely used in the industries such as papermaking, weaving, medicine, environmental protection.In recent years, China's hydrogen peroxide industry is developed rapidly, and its production capacity is with annual 15% speed increment, and the whole nation is built and surpassed 7,000,000 tons/year (with concentration 27.5%, calculating) building production capacity at present.In addition along with the rapid popularization of hydrogen peroxide in the synthetic field of various green chemical industries, especially the application in the technology such as hydrogen peroxide preparing epoxypropane by epoxidation of propene (HPPO technology) and green caprolactam be synthetic, makes China's hydrogen peroxide industry obtain new development opportunity.
The main stream approach that hydrogen peroxide is produced is at present anthraquinone, with suitable organic solvent dissolution working material (alkyl-anthraquinone), be configured to working solution, under the effect of catalyst and hydrogen, anthraquinone hydrogenation reduction generates anthrahydroquinone, then through air or oxygen Oxidation Anthracene quinhydrones, become anthraquinone again, obtain hydrogen peroxide simultaneously.Utilize pure water the working solution that contains hydrogen peroxide to be extracted to the aqueous solution that obtains hydrogen peroxide, raffinate be working solution after filtration, return to hydrogenation process and proceed hydrogenation reaction after regeneration.Hydrogenating alkyl anthraquinone is the core procedure that hydrogen peroxide is produced, and hydrogenation technique used comprises stirred tank hydrogenation technique, fixed bed hydrogenation technique, fluidized-bed hydrogenation technique.Because the catalyst based stirred tank anthraquinone hydrogenation of Ni technique exists production scale little, automaticity is low, poor stability, and the reasons such as complicated operation, are eliminated now substantially; Although fluid bed anthraquinone hydrogenation technique has production capacity large, hydrogenation efficiency advantages of higher, hydrogenation reactor is difficult to promote on a large scale at home owing to relating to patent problem at present; Fixed bed anthraquinone hydrogenation technique is because hydrogenation plant is simple, and plant capacity is large, security of operation, the feature such as simple to operate, makes this technique remain the main flow technique that domestic hydrogen peroxide is produced.
Fixed bed anthraquinone hydrogenation technique catalyst used is loaded catalyst, conventionally the porous masses such as aluminium oxide, silica, zirconia, magnesia of take are carrier, the form of carrier can be spherical, bar shaped or abnormity etc., and the noble metals such as palladium, platinum, ruthenium are active component.At present industrial the most frequently used be the spheric catalyst of alumina load palladium.For spheric catalyst, the distribution situation according to active component on carrier, can be divided into eggshell type, protein type, yolk type and even type.Because anthraquinone hydrogenation is interior diffusion controlled reaction, adopt egg-shell catalyst to be conducive to improve anthraquinone hydrogenation speed, and be conducive to product and from catalyst surface, come off in time, avoid further hydrogenation to cause anthraquinone degraded.
At present about the application of anthraquinone hydrogenation fixed bde catalyst a large amount of patents: patent CN102389799B disclose a kind of on ball-aluminium oxide carrier a small amount of alkali metal of first load or transition metal salt, the main active component palladium of load again after drying roasting, then obtains Pd loaded catalyst through high-temperature roasting, reducing agent reduction; Patent CN1259483A discloses a kind of at TiO
2-Al
2o
3load 0.1-0.3%Pt, 0.1-0.5%Ni or Co or Ru on complex carrier, 0.01-0.1%Ca, Mg component, make precious metals pt loaded catalyst through dipping, dry, roasting, reduction; Patent CN1172744C disclose a kind of by alumina support in rare-earth metal nitrate solution, under 20-40kHz ultrasound condition, flood, pass through afterwards roasting, PdCl
2solution incipient impregnation, and in ice-water bath, drip the KBH of 1mol/L
4solution, then be prepared into Pd loaded catalyst through washing; Patent CN101462052A discloses a kind of employing equal-volume co-impregnation or two step phenol infusion processes are prepared Pd-MOx/ γ-Al
2o
3, wherein M represents Cr, Zr, Mn; Patent CN1175931C discloses a kind of ball-aluminium oxide loaded palladium catalyst, alumina globule applies appropriate rare earth oxide in advance, the presoma of rare earth oxide used is nitrate or the acetate of single light rare earth La, Ce, Pr, Nd, Sm, after 900-1000 ℃ of high-temperature roasting, carry out impregnation process, after dipping, drying and calcining obtains catalyst again.
The problem that above-mentioned patent exists is mainly that catalytic component is complicated, and preparation process is loaded down with trivial details, has improved the production cost of catalyst; Most of catalyst directly carry out drying and calcining operation after dip operation in addition, and experiment shows, can make like this catalyst surface residual impurity ion, thus covering catalyst Active sites, the hydrogenation activity of reduction catalyst.
Summary of the invention
The present invention is for solving the problems of the technologies described above, provide a kind of activity high, selectively good, active metal consumption is few, the preparation method of the simple eggshell type anthraquinone hydrogenation of preparation method fixed bde catalyst, the concrete technical scheme of employing is as follows:
A preparation method for eggshell type anthraquinone hydrogenation fixed bde catalyst, comprises the steps:
Step 1: by spherical Al
2o
3carrier is the dry 6-12h that processes at 150-200 ℃, to remove the moisture that is attached to carrier surface;
Step 2: by a certain amount of PdCl
2mix with watery hydrochloric acid, and under the water bath condition of 50-90 ℃ abundant stirring and dissolving, form the chlorine palladium acid solution of 0.001-0.1g/mL, maceration extract pH is adjusted to 3-5;
Step 3: by the spherical Al through step 1 pre-dried
2o
3carrier is put into the 0.001-0.1g/mL chlorine palladium acid solution that step 2 makes and is carried out supersaturation dipping, and supersaturation dip operation is to carry out 0.5-2h under the condition of 30-90 ℃ at bath temperature; The too low meeting of bath temperature causes flooding inhomogeneous, and the too high meeting of bath temperature causes impregnate layer too thick;
Step 4: after dipping finishes, with desalted water, catalyst is washed, washing operation temperature is 30-90 ℃, desalination electrical conductivity of water <1 μ S/cm, the electrical conductivity of final washes is at 2-6 μ S/cm; Washing operation carries out operating efficiency to be reached to the highest at 30-90 ℃, and at other temperature, carrying out washing operation efficiency can decrease;
Step 5: be dried 1-5h after catalyst detergent finishes at 100-150 ℃, then at 400-600 ℃ of calcining 2-10h; The too high or too low drying effect that all can cause of baking temperature is bad, reduces catalyst finally active; And calcining heat is low, can cause calcining not exclusively, calcining heat is too high, can cause catalyst to burn, and both can reduce the final activity of catalyst;
Step 6: after calcining, catalyst is reduced under pure hydrogen environment, reduction temperature 30-100 ℃, recovery time 12-24 hour; At other temperature or long or shorter recovery time, all can make catalyst reduction insufficient, affect finally activity of catalyst.
The catalyst making according to described method is by spherical Al
2o
3carrier and active component form, described spherical Al
2o
3carrier is δ-Al
2o
3, θ-Al
2o
3or δ-, θ-the spherical Al of multiphase
2o
3, specific area is 50-200m
2/ g, pore volume is 0.2-1.5ml/g, average pore size is 10-30nm, bulk density 0.3-0.5g/ml, Na content <0.1%, Fe content <0.1%, carrier granularity 2-5mm, compression strength >30N/; Described active component is Metal Palladium.
Described active component is at spherical Al
2o
3load capacity on carrier is 0.1-0.3wt%.
The regulator solution of pH described in step 2 is 0.1-1mol/L NaOH, sodium carbonate, potash or potassium hydroxide solution.
Described in step 3, the liquid-solid ratio of supersaturation dip operation is 1.2-1.8.Described liquid-solid ratio is the amount of maceration extract and the ratio of carrier saturated water adsorptive value.Liquid-solid ratio < 1.2, flood inhomogeneous; Liquid-solid ratio > 1.8 can cause the palladium in maceration extract all not load on carrier, causes palladium loss.
Described in step 3, supersaturation dip operation bath temperature is preferably 50-80 ℃.This temperature range dipping effect is best, and prepared catalyst hydrogenation activity is best.
The preferred 50-80 ℃ of washing operation temperature described in step 4.This temperature range dipping effect is best, and prepared catalyst hydrogenation activity is best.After catalyst soakage, carry out washing operation and have positive role to improving the hydrogenation efficiency of catalyst, the object of washing is to remove sodium ion, chlorion or other foreign ions that is attached to catalyst surface, it is finally active that washing deficiency or overwass all can affect catalyst, therefore catalyst detergent need to be controlled by the electrical conductivity to washes, thereby controls whole washing process.Overwass can cause catalyst surface active Metal Palladium to run off, and lowers hydrogenation efficiency.
The active metal palladium of eggshell type anthraquinone hydrogenation fixed bde catalyst of the present invention is attached to catalyst outer surface closely, be eggshell type and distribute, impregnate layer thickness, i.e. the thickness 50-80 μ m of active metal palladium, be conducive to the efficient utilization of precious metal palladium, catalyst activity is high.
Evaluating catalyst of the present invention working solution used is dissolved in the mixed solvent of pseudocumene and trioctyl phosphate by 2-EAQ and 2-ethyl tetrahydro-anthraquinone, ratio of solvent is 75:25, effective anthraquinone total concentration is 120g/L, wherein 2-EAQ is EAQ30.46g/L, and 2-ethyl tetrahydro-anthraquinone is H4EAQ89.54g/L.Hydrogenation fixed bed reactors diameter 12mm, length 200mm, the additional cover water bath with thermostatic control heating of reactor, working solution and hydrogen from reactor head enter and flow and through beds, the flow velocity of working solution and hydrogen is controlled by measuring pump and mass flowmenter respectively, catalyst addition 15ml, reaction pressure 0.3MPa, 50 ℃ of hydrogenation temperatures, working solution air speed 10h
-1, hydrogen gas space velocity 100h
-1, described air speed is volume space velocity.After hydrogenation, take out 5ml hydride be placed in separatory funnel and be fully oxidized with pure oxygen from reactor sample tap, the hydrogen peroxide being generated by Standard Potassium Permanganate Solution titration after extraction, calculates the hydrogenation efficiency of catalyst thus, and hydrogenation efficiency E is calculated as follows:
E=V
1×C×34.02/2V
2
In formula: E is the mass concentration g/L with the hydrogen peroxide of hydride equivalent
V1 is the titration volume L of Standard Potassium Permanganate Solution
C is the actual concentrations mol/L of Standard Potassium Permanganate Solution
V2 is sample volume ml
34.02 is the relative molecular mass of hydrogen peroxide
By liquid chromatography, measure catalyst selectivity.The ratio that selectively refers to effective anthraquinone (2-EAQ+2-ethyl tetrahydro-anthraquinone) content and general anthraquinone (effective anthraquinone+degraded anthraquinone) content in working solution.Described degraded anthraquinone is for effective anthraquinone, effective anthraquinone mainly refers to 2-EAQ+2-ethyl tetrahydro-anthraquinone, energy Hydrogen Peroxide after these two kinds of anthraquinone hydrogenations, oxidation, and degraded anthraquinone (as 2-ethyl six hydrogen anthraquinones, 2-ethyl octahydro anthraquinone) cannot Hydrogen Peroxide after hydrogenation, oxidation.
The invention has the beneficial effects as follows:
Catalyst preparation process is simple, and production cost is low, and hydrogenation efficiency is high, selectively good, hydrogenation efficiency >9g/L, selective >99.5%; The active metal palladium close attachment of catalyst, at catalyst outer surface, is eggshell type and distributes, and impregnate layer thickness 50-80 μ m, is conducive to the efficient utilization of precious metal palladium.In catalyst preparation process, introduce washing procedure, and washing process is quantized.
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below the specific embodiment of the present invention is described further, but does not limit protection scope of the present invention.
Embodiment 1:
Take 10g ball-aluminium oxide carrier, carrier is θ-Al
2o
3, specific area is 98m
2/ g, pore volume 0.5ml/g, average pore size 14nm, bulk density 0.45g/ml, Na content 0.07%, Fe content 0.07%, particle diameter 2-3mm, compression strength 50N/, and at 150 ℃, ball-aluminium oxide is dried and processes 12h.By a certain amount of palladium bichloride PdCl
2mix with watery hydrochloric acid, and under the water bath condition of 50 ℃ abundant stirring and dissolving, form the chlorine palladium acid solution of 0.003g/mL, then with the sodium hydroxide solution of 1mol/L, the acid-base value of above-mentioned solution is regulated, make the pH=3.0 of final chlorine palladium acid solution, this solution is maceration extract.Aforementioned 10g ball-aluminium oxide carrier is put into the above-mentioned maceration extract of 20ml, under the water bath condition of 30 ℃, carry out 2h.After dipping finishes, with the desalted water that electrical conductivity is 0.5 μ S/cm, catalyst is washed, until the electrical conductivity of washes is 4.5 μ S/cm, stop washing operation, washing is carried out at 30 ℃.After catalyst detergent finishes, at 100 ℃, be dried 5h, and then at 500 ℃ of calcining 10h, after calcining, catalyst reduced under pure hydrogen atmosphere, 30 ℃ of reduction temperatures, 12 hours recovery times, can make anthraquinone hydrogenation fixed bde catalyst.
Embodiment 2:
Take 10g ball-aluminium oxide carrier, carrier is δ-Al
2o
3, specific area is 150m
2/ g, pore volume 1.2ml/g, average pore size 11nm, bulk density 0.5g/ml, Na content 0.05%, Fe content 0.05%, particle diameter 3mm, compression strength 30N/, and at 180 ℃, ball-aluminium oxide is dried and processes 12h.By a certain amount of palladium bichloride PdCl
2mix with watery hydrochloric acid, and under the water bath condition of 60 ℃ abundant stirring and dissolving, form the chlorine palladium acid solution of 0.0032g/mL, then with the sodium hydroxide solution of 0.5mol/L, the acid-base value of above-mentioned solution is regulated, make the pH=3.5 of final chlorine palladium acid solution, this solution is maceration extract.Aforementioned 10g ball-aluminium oxide carrier is put into the above-mentioned maceration extract of 20ml, under the water bath condition of 50 ℃, carry out 45min.After dipping finishes, with the desalted water that electrical conductivity is 0.5 μ S/cm, catalyst is washed, until the electrical conductivity of washes is 5.5 μ S/cm, stop washing operation, washing is carried out at 40 ℃.After catalyst detergent finishes, at 110 ℃, be dried 1h, and then at 550 ℃ of calcining 4h, after calcining, catalyst reduced under pure hydrogen atmosphere, 30 ℃ of reduction temperatures, 12 hours recovery times, can make anthraquinone hydrogenation fixed bde catalyst.
Embodiment 3:
Take 10g ball-aluminium oxide carrier, carrier is δ-θ-multiphase Al
2o
3, specific area is 70m
2/ g, pore volume 0.3ml/g, average pore size 25nm, bulk density 0.5g/ml, Na content 0.05%, Fe content 0.05%, particle diameter 2.8mm, compression strength 50N/, and at 170 ℃, ball-aluminium oxide is dried and processes 6h.By a certain amount of palladium bichloride PdCl
2mix with watery hydrochloric acid, and under the water bath condition of 70 ℃ abundant stirring and dissolving, form the chlorine palladium acid solution of 0.004g/mL, then with the sodium carbonate liquor of 1mol/L, the acid-base value of above-mentioned solution is regulated, make the pH=4.0 of final chlorine palladium acid solution, this solution is maceration extract.Aforementioned 10g ball-aluminium oxide carrier is put into the above-mentioned maceration extract of 18ml, under the water bath condition of 60 ℃, carry out 45min.After dipping finishes, with the desalted water that electrical conductivity is 0.5 μ S/cm, catalyst is washed, until the electrical conductivity of washes is 3.59 μ S/cm, stop washing operation, washing is carried out at 30 ℃.After catalyst detergent finishes, at 110 ℃, be dried 1h, and then at 580 ℃ of calcining 4h, after calcining, catalyst reduced under pure hydrogen atmosphere, 30 ℃ of reduction temperatures, 12 hours recovery times, can make anthraquinone hydrogenation fixed bde catalyst.
Embodiment 4
Take 10g ball-aluminium oxide carrier, carrier is θ-Al
2o
3, specific area is 180m
2/ g, pore volume 1.5ml/g, average pore size 12nm, bulk density 0.45g/ml, Na content 0.06%, Fe content 0.06%, particle diameter 2-3mm, compression strength 55N/, and at 170 ℃, ball-aluminium oxide is dried and processes 10h.By a certain amount of palladium bichloride PdCl
2mix with watery hydrochloric acid, and under the water bath condition of 80 ℃ abundant stirring and dissolving, form the chlorine palladium acid solution of 0.0035g/mL, then with the sodium carbonate liquor of 1mol/L, the acid-base value of above-mentioned solution is regulated, make the pH=4.5 of final chlorine palladium acid solution, this solution is maceration extract.Aforementioned 10g ball-aluminium oxide carrier is put into the above-mentioned maceration extract of 18ml, under the water bath condition of 80 ℃, carry out 30min.After dipping finishes, with the desalted water that electrical conductivity is 0.5 μ S/cm, catalyst is washed, until the electrical conductivity of washes is 5 μ S/cm, stop washing operation, washing is carried out at 50 ℃.After catalyst detergent finishes, at 110 ℃, be dried 5h, and then at 500 ℃ of calcining 10h, after calcining, catalyst reduced under pure hydrogen atmosphere, 30 ℃ of reduction temperatures, 12 hours recovery times, can make anthraquinone hydrogenation fixed bde catalyst.
Embodiment 5
Take 10g ball-aluminium oxide carrier, carrier is θ-Al
2o
3, specific area is 80m
2/ g, pore volume 1.0ml/g, average pore size 20nm, bulk density 0.4g/ml, Na content 0.05%, Fe content 0.05%, particle diameter 2.5mm, compression strength 40N/, and at 130 ℃, ball-aluminium oxide is dried and processes 8h.By a certain amount of palladium bichloride PdCl
2mix with watery hydrochloric acid, and under the water bath condition of 75 ℃ abundant stirring and dissolving, form the chlorine palladium acid solution of 0.0027g/mL, then with the sodium carbonate liquor of 0.5mol/L, the acid-base value of above-mentioned solution is regulated, make the pH=3.0 of final chlorine palladium acid solution, this solution is maceration extract.Aforementioned 10g ball-aluminium oxide carrier is put into the above-mentioned maceration extract of 20ml, under the water bath condition of 40 ℃, carry out 2h.After dipping finishes, with the desalted water that electrical conductivity is 0.5 μ S/cm, catalyst is washed, until the electrical conductivity of washes is 3.0 μ S/cm, stop washing operation, washing is carried out at 80 ℃.After catalyst detergent finishes, at 110 ℃, be dried 4h, and then at 500 ℃ of calcining 10h, after calcining, catalyst reduced under pure hydrogen atmosphere, 30 ℃ of reduction temperatures, 12 hours recovery times, can make anthraquinone hydrogenation fixed bde catalyst.
More than the embodiment for carrying out according to the method for the invention, exemplifies two below and does not carry out washing step and change washing step desalted water controlling the comparative example in the situation of parameter, and itself and the embodiment of the present invention are contrasted.
Comparative example 1:
With the same method Kaolinite Preparation of Catalyst of embodiment 1, just after catalyst soakage, do not carry out washing operation, be directly dried, calcining, restoring operation, make catalyst.
Comparative example 2:
With the same method Kaolinite Preparation of Catalyst of embodiment 2, different is after catalyst soakage finishes, with the desalted water that electrical conductivity is 0.5 μ S/cm, catalyst is washed, until being 1.5 μ S/cm, the electrical conductivity of washes stops washing operation, then be dried, calcining, restoring operation, make catalyst.
Based on evaluation method described in summary of the invention, evaluate, the anthraquinone hydrogenation fixed bde catalyst that above-described embodiment is made is evaluated, and acquired results is listed as follows:
Table 1 eggshell type anthraquinone hydrogenation fixed bde catalyst evaluation result
| Embodiment | Palladium load capacity/% | Hydrogenation efficiency/g/L | Selectively/% |
| Embodiment 1 | 0.244 | 9.3 | 99.6 |
| Embodiment 2 | 0.268 | 9.42 | 99.6 |
| Embodiment 3 | 0.290 | 9.6 | 99.5 |
| Embodiment 4 | 0.285 | 9.4 | 99.5 |
| Embodiment 5 | 0.220 | 9.1 | 99.5 |
| Comparative example 1 | 0.255 | 6.8 | 99.1 |
| Comparative example 2 | 0.252 | 8.4 | 99.3 |
Known according to above embodiment experimental data, the eggshell type anthraquinone hydrogenation fixed bde catalyst hydrogenation efficiency making according to the method for the invention is high, selectively good.
After embodiment 1 and comparative example 1 explanation catalyst soakage, carry out washing operation favourable to the hydrogenation efficiency of raising catalyst.
The washing procedure of embodiment 2 and comparative example 2 explanation catalyst need to be controlled, and overwass can cause catalyst surface active Metal Palladium to run off, and lowers hydrogenation efficiency.
Preparation method of the present invention is described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, process conditions and realize corresponding other object, its relevant change does not all depart from content of the present invention, within all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included in scope of the present invention.
Claims (7)
1. a preparation method for eggshell type anthraquinone hydrogenation fixed bde catalyst, is characterized in that, comprises the steps:
Step 1: by spherical Al
2o
3carrier is the dry 6-12h that processes at 150-200 ℃, to remove the moisture that is attached to carrier surface;
Step 2: by a certain amount of PdCl
2mix with watery hydrochloric acid, and under the water bath condition of 50-90 ℃ abundant stirring and dissolving, form the chlorine palladium acid solution of 0.001-0.1g/mL, maceration extract pH is adjusted to 3-5;
Step 3: by the spherical Al through step 1 pre-dried
2o
3carrier is put into the 0.001-0.1g/mL chlorine palladium acid solution that step 2 makes and is carried out supersaturation dipping, and supersaturation dip operation is to carry out 0.5-2h under the condition of 30-90 ℃ at bath temperature;
Step 4: after dipping finishes, with desalted water, catalyst is washed, washing operation temperature is 30-90 ℃, desalination electrical conductivity of water <1 μ S/cm, the electrical conductivity of final washes is at 2-6 μ S/cm;
Step 5: be dried 1-5h after catalyst detergent finishes at 100-150 ℃, then at 400-600 ℃ of calcining 2-10h;
Step 6: after calcining, catalyst is reduced under pure hydrogen environment, reduction temperature 30-100 ℃, recovery time 12-24 hour.
2. a kind of preparation method of eggshell type anthraquinone hydrogenation fixed bde catalyst according to claim 1, is characterized in that, the catalyst making according to described method is by spherical Al
2o
3carrier and active component form, described spherical Al
2o
3carrier is δ-Al
2o
3, θ-Al
2o
3or δ-, θ-the spherical Al of multiphase
2o
3, specific area is 50-200m
2/ g, pore volume is 0.2-1.5ml/g, average pore size is 10-30nm, bulk density 0.3-0.5g/ml, Na content <0.1%, Fe content <0.1%, carrier granularity 2-5mm, compression strength >30N/; Described active component is Metal Palladium.
3. a kind of preparation method of eggshell type anthraquinone hydrogenation fixed bde catalyst according to claim 2, is characterized in that, described active component is at spherical Al
2o
3load capacity on carrier is 0.1-0.3wt%.
4. a kind of preparation method of eggshell type anthraquinone hydrogenation fixed bde catalyst according to claim 1, is characterized in that, the regulator solution of pH described in step 2 is 0.1-1mol/L NaOH, sodium carbonate, potash or potassium hydroxide solution.
5. a kind of preparation method of eggshell type anthraquinone hydrogenation fixed bde catalyst according to claim 1, is characterized in that, the liquid-solid ratio of supersaturation dip operation is 1.2-1.8 described in step 3.
6. a kind of preparation method of eggshell type anthraquinone hydrogenation fixed bde catalyst according to claim 1, is characterized in that, supersaturation dip operation bath temperature 50-80 ℃ described in step 3.
7. a kind of preparation method of eggshell type anthraquinone hydrogenation fixed bde catalyst according to claim 1, is characterized in that, washing operation temperature 50-80 ℃ described in step 4.
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| CN108057438A (en) * | 2017-09-06 | 2018-05-22 | 贵研工业催化剂（云南）有限公司 | It is a kind of to prepare ruthenium catalyst of hydrogen peroxide and preparation method thereof for anthraquinone hydrogenation |
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| CN115672322A (en) * | 2022-10-12 | 2023-02-03 | 中国石油大学(华东) | A kind of Cu-based eggshell catalyst, preparation method and method for hydrogenation of oxalic acid diester |
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