CN1435277A - Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof - Google Patents
Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof Download PDFInfo
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- CN1435277A CN1435277A CN 03115503 CN03115503A CN1435277A CN 1435277 A CN1435277 A CN 1435277A CN 03115503 CN03115503 CN 03115503 CN 03115503 A CN03115503 A CN 03115503A CN 1435277 A CN1435277 A CN 1435277A
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- catalyst
- anthraquinone
- hydrogen peroxide
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Abstract
A carried Pd-alumina catalyst for preparing hydrogen peroxide by anthraquinone method is prepared from Pd as main active component and Al2O3 as carrier through impregnation. Said Al2O3 has been coated by RE oxide and calcined at 900-1000 deg.C. It has high hydrogenating efficiency of 8-9 gH2O2/L for 2-ethyl anthraquinone/heavy arene plus trioctyl phosphate or 10-13 gH2O2/L for (2-tert-butyl anthraquinone plus 2-ethyl anthraquinone)/(heavy arene plus tetrabutyl urea).
Description
Technical field:
The present invention relates to a kind of with pre-soaked Sq rare earth oxide, and through 900-1000 ℃ of hard burned Al
2O
3Being carrier, is process for prepairng hydrogen peroxide by anthraquinone support type hydrogenation catalyst of main active component and preparation method thereof with palladium.Exactly, it belongs to a kind of metallic catalyst and preparation method thereof.
Background technology:
Anthraquinone is large-scale production H in the world at present
2O
2The most widely used method.Carrying alumina palladium or other platinum metal catalysts then are the most frequently used hydrogenation catalysts of this technology.In order constantly to improve the performance of catalyst, reduce the consumption of expensive platinum group metal, people are doing a large amount of work aspect the selection of the impregnation technology of platinum group metal (as palladium) and carrier and the modification for a long time.
By retrieval as can be known: U.S. Patent number US 4,061,598 (open day 1977.12.6), it discloses a kind of preparation method of palladium-aluminium oxide catalyst.This patent is used γ-Al
2O
3Or δ-, θ-aluminium oxide is carrier, earlier with an amount of wet chemical oxide impregnation alumina supporter, but keep carrier surface not wetted, with the accurate weighing of process, the dried sodium chloride palladium salt of grinding mixes after 30 minutes with above-mentioned alumina support at room temperature to be shelved 48 hours more then.With hydrazine aqueous solution reducing catalyst and to spend deionised water catalyst to wash water pH value be 7, after evening, in air atmosphere, handled 4 hours in 550 ℃ 30 ℃ of dryings.The palladium weight content of this catalyst is 0.3-5.0%, it is said that this catalyst has good operation lifetime and higher activity.Chinese invention patent publication number CN1259483A (open day a 2000.7.12) has announced a kind of with through 950 ℃ of baked aluminium oxide or TiO
2-Al
2O
3Composite oxides are carrier, are maceration extract with the saline solution of Pt, Ni, Co, Ru, with citric acid, maleic acid, acetic acid, lactic acid etc. as striving adsorbent unexpectedly, with catalyst prepared with H
2-N
2The gas reduction.The platinum weight content of this catalyst is 0.1-0.5%.It is said that this catalyst has characteristics such as high activity and high selectivity.With rare earth oxide as the carrier of platinum metal catalysts and be used for H
2O
2Synthetic have (day) spy to open flat 4-238802 (open day 1992.8.26) to have used cerium oxide be that to open flat 4-285003 (openly day 1992.10.9) be carrier with lanthana for carrier and (day) spy.But they all are as hydrogen, the directly synthetic H of oxygen
2O
2The catalyst of technology is not seen the relevant report that is useful on anthraquinone process.
Summary of the invention:
The object of the present invention is to provide a kind of with process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst and preparation method thereof, i.e. a kind of Catalyst for Hydrogenation of Anthraquinone and preparation method thereof.This catalyst is guaranteeing that preferably bullion content reduces about 30% than similar catalyst under the catalytic performance and the prerequisite in life-span.
Task of the present invention is:
The hydrogenation catalyst that a kind of alkyl-anthraquinone is produced hydrogen peroxide is to be carrier with coated rare earth oxide in advance and through the aluminium oxide of 900-1000 ℃ of high-temperature calcination, and it is 0.1-15%wt that rare earth oxide is coated with complexor; With palladium is main active ingredient, and loading is 0.15-0.25%wt.
Preparation process comprises the steps: (a) with rare earth nitrades or acetate solution impregnation of alumina carrier, and at temperature 500-1000 ℃ rare earth salts is converted into oxide; (b) an amount of palladium bichloride and etc. weight sodium chloride be dissolved in certain water gaging and be made into the sodium chloride aqueous palladium; (c) with a certain amount of dried rare earth oxide that soaked in advance, the BET surface area is 60-130m
2The aluminium oxide of/g adds in the sodium chloride palladium solution, or sodium chloride palladium solution is added in the aluminium oxide; (d) isolate catalyst and can't check chlorion with 2% liquor argenti nitratis ophthalmicus with pure water washing catalyst to wash water till; (e) catalyst after the washing was handled about 4-6 hour in 450-550 ℃ in air atmosphere after 80-120 ℃ of oven dry again; (f) catalyst is with hydrogen-containing gas or hydrazine hydrate aqueous solution or alkaline formaldehyde solution reduction.If during with hydrazine hydrate or alkaline formaldehyde solution reduction, follow-up washing step must be arranged, be 7 until the pH of wash water value.
The specific embodiment:
Preparation of catalysts method of the present invention adopts immersion process for preparing, can be divided into high temperature (50-98 ℃) infusion process and room temperature (10-35 ℃) infusion process with the height of maceration extract temperature.Impregnating equipment can use conventional dipping tank.Preparation process comprises the steps: that (a) is with a certain amount of, certain density rare earth nitrades or acetate solution coated alumina support.Used alumina support is δ-Al
2O
3, θ-Al
2O
3, or δ-, θ-mixing phase alumina, its BET surface area is 60-130m
2/ g, average pore radius is about 10-14nm, Na
2O content＜0.05%.The precursor of rare earth oxide is nitrate, the acetate of nitrate, acetate or their mixtures of single light rare earth La, Ce, Pr, Nd, Sm.Soaking aluminium oxide after the salt about 80-120 ℃ of oven dry 2 hours down, under about 500-1000 ℃ temperature the rare earth salts on the aluminium oxide being calcined becomes rare earth oxide again.Rare earth salts solution also can be coated with and be loaded in γ-Al
2O
3On, when carrying out the alumina high temperature phase inversion, become rare earth oxide then.The oven dry of catalyst of the present invention and calcining can be adopted the method for any routine, and oven dry and calciner are not had specific (special) requirements, but should avoid in operation bringing the impurity harmful to catalyst into, as sulphur, phosphorus etc.(b) an amount of palladium bichloride and etc. weight sodium chloride be dissolved in certain water gaging and be made into certain density sodium chloride aqueous palladium.(c) aluminium oxide of a certain amount of dried rare earth oxide of coated is in advance added in the sodium chloride palladium solution of Sq (or add in aluminium oxide sodium chloride palladium solution), in Metal Palladium, the loading of palladium is 0.15-0.25%wt, and the thickness of palladium layer is 30-80 μ m.(d) isolate catalyst and can't check chlorion with 2% liquor argenti nitratis ophthalmicus with pure water washing catalyst to wash water till.(e) catalyst after the washing was handled about 4-6 hour in 450-550 ℃ in air atmosphere after 80-120 ℃ of oven dry again.(f) catalyst is with hydrogen-containing gas or hydrazine hydrate aqueous solution or alkaline formaldehyde solution reduction.If during with hydrazine hydrate or alkaline formaldehyde solution reduction, follow-up washing step must be arranged, be 7 until the pH of wash water value.
The precursor of the main active substances Metal Palladium of catalyst of the present invention is a palladium bichloride.The solvent of relevant solution is a water.
Carrier carries palladium can adopt disposable dipping, also can adopt repeatedly the method for dipping to carry out, and when adopting the high temperature infusion process, should use the repeatedly method of dipping.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Take by weighing 30g γ-Al
2O
3Be carrier, its shape and size are φ 3 * 5-20 (mm) column, impurity Na
2O＜0.05%wt, the BET surface area is about 116m
2/ g places the glass beaker of a 250ml.Is 18ml concentration 0.2046mol/l, and temperature is the La (NO of room temperature
3)
3The aqueous solution is poured in the above-mentioned aluminium oxide and is stirred and makes its uniform absorption.Place baking oven in about 60 minutes of about 80-120 ℃ of dehydration in the aluminium oxide behind the absorption rare earth nitrate aqueous solution, be transplanted on then in the high temperature furnace under air atmosphere, reduce to room temperature in 800～1000 ℃ of calcinings after 2～10 hours, the rare earth oxide appendix amount on the aluminium oxide is about 2%wt.
To place the glass beaker of a 250ml through the alumina support after the above-mentioned processing, pouring 60ml concentration into is that 0.00515mol/l, temperature are about 98 ℃ Na
2PdCl
4Solution flooded 3 minutes, after leaching catalyst and draining, be placed in the drying box in 80-120 ℃ down oven dry take out after 60 minutes and place glass beaker again, pouring 60ml concentration again into is that 0.00515mol/l, temperature are about 98 ℃ Na
2PdCl
4Solution flooded 3 minutes, after leaching catalyst and draining, was washed till wash water 2%AgNO with deionized water
3Solution can't check till the chlorion.Leach catalyst and drain, after the about 4-6 of roasting hour, be cooled to room temperature through about 2 hours of 80-150 ℃ of oven dry and in high temperature furnace in 450-550 ℃, air atmosphere, promptly make required catalyst, its Metal Palladium weight content is 0.201%.
Catalyst adopts micro fixed-bed reactor to estimate (seeing " University of Fuzhou's journal (natural science edition) " the 4th phase in 2000).50 ℃ of reaction temperatures, pressure is normal pressure, mixing speed is 1400r/min, sources of hydrogen employing hydrogen nitrogen ratio is 3: 1 a hydrogen nitrogen mixed gas, gas flow is 1 liter/minute, the catalyst loading amount is the about 40ml of 20g, and active testing procatalyst original position in reactor was reduced 8 hours at 60-80 ℃ with hydrogen nitrogen mixed gas.The working solution composition that this experiment is used is: 2-EAQ (EAQ) content 130g/l, and solvent adopts the mixture of trioctyl phosphate (TOP) and heavy aromatics, and ratio is 25/75, and the working solution consumption is 240ml.
The hydrogenation rate constant of this catalyst of evaluation result is 10.953 * 10
-2Mol/h.l, hydrogen are imitated and are 9.5g H
2O
2/ l, catabolite＜0.5g/kgH
2O
2(27.5%).
Embodiment 2
Repeat the process of embodiment 1, just use rare earth salts solution instead Nd (NO that 18ml concentration is 0.1023mol/l
3)
3The aqueous solution.The weight content of rare earth oxide is about 1% on the carrier, and the Metal Palladium weight content is 0.205%.
This catalyst adopts the condition evaluating identical with embodiment 1, and its hydrogenation rate constant is: 10.492 * 10
-2Mol/h.l; Hydrogen is imitated: 9.1g H
2O
2/ l; Catabolite＜0.5g/kgH
2O
2(27.5%).
Embodiment 3
Taking by weighing the 30g particle diameter is φ 3 ± 0.2mm, impurity Na
2O＜0.05%wt, the BET surface area is about 105m
2Spherical gamma-Al of/g
2O
3, place the 250ml glass beaker.Is 30ml concentration 0.06138mol/l, and temperature is the La (CH of room temperature
3COOH)
3The aqueous solution is poured in the above-mentioned aluminium oxide and is stirred and makes its uniform absorption.Place baking oven in about 60 minutes of about 80-120 ℃ of dehydration in the aluminium oxide behind the absorption lanthanon acetate aqueous solution, be transplanted on then in the high temperature furnace under air atmosphere, reduce to room temperature in 800～1000 ℃ of calcinings after 2～8 hours, the rare earth oxide appendix amount on the aluminium oxide is about 1%wt.
To place the glass beaker of a 250ml through the alumina support after the above-mentioned processing, pouring 70ml concentration into is that 0.008822mol/l, temperature are the Na of room temperature
2PdCl
4Solution under agitation, flooded about 60 minutes, after leaching catalyst and draining, was washed till wash water 2%AgNO with the deionized water that flows
3Solution can't check till the chlorion.Leach catalyst and drain, after the about 4-6 of roasting hour, be cooled to room temperature through 80-150 ℃ of oven dry 2 hours and in high temperature furnace in 450-550 ℃, air atmosphere, promptly make required catalyst, its Metal Palladium weight content is 0.1995%.
The evaluating apparatus of this routine catalyst, method follow embodiment 1 identical with condition.But the working media working concentration of working solution is the 2-tert-butyl group anthraquinone (BAQ) of 202g/l and the mixture of EAQ, EAQ/BAQ=1.78, and solvent uses the mixture of tetrabutyl urea (TBU) and heavy aromatics, and the ratio of the two is 25/75.
The hydrogenation rate constant of this catalyst of evaluation result is 11.759 * 10
-2Mol/h.l, hydrogen are imitated and are 13.5g H
2O
2/ l, catabolite＜0.4g/kgH
2O
2(27.5%).
Comparative example
The commercially available spherical Pd/Al of 20g
2O
3Catalyst, particle diameter is about 3mm, and Metal Palladium content is 0.284%wt, estimates under the condition identical with embodiment 1, and the hydrogenation rate constant of this catalyst is 9.094 * 10
-2Mol/h.l, hydrogen are imitated and are 8.7g H
2O
2/ l, catabolite＜0.5g/kgH
2O
2(27.5%).
Claims (9)
1. one kind with process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst and preparation method thereof, it is characterized in that: the hydrogenation catalyst that alkyl-anthraquinone is produced hydrogen peroxide is to be carrier with coated rare earth oxide in advance and through the aluminium oxide of 900-1000 ℃ of high-temperature calcination, it is 0.1-15%wt that rare earth oxide is coated with complexor, with palladium is main active ingredient, and loading is 0.15-0.25%wt.
2. according to the described a kind of preparation method of claim 1 with the process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst, it is characterized in that: preparation process comprises the steps: (a) with rare earth nitrades or acetate solution impregnation of alumina carrier, and at temperature 500-1000 ℃ rare earth salts is converted into oxide; (b) an amount of palladium bichloride with wait the sodium chloride of weight to be dissolved in certain water gaging with it to be made into the sodium chloride aqueous palladium; (c) with a certain amount of dried rare earth oxide that soaked in advance, the BET surface area is 60-130m
2The aluminium oxide of/g adds in the sodium chloride palladium solution, or sodium chloride palladium solution is added in the aluminium oxide; (d) isolate catalyst and can't check chlorion with 2% liquor argenti nitratis ophthalmicus with pure water washing catalyst to wash water till; (e) catalyst after the washing was handled about 4-6 hour in 450-550 ℃ in air atmosphere after 80-120 ℃ of oven dry again.
3. a kind of preparation method with the process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst according to claim 2, it is characterized in that: used alumina support is δ-Al
2O
3, θ-Al
2O
3, or δ-, θ-mixing phase alumina, its BET surface area is 60-130m
2/ g, average pore radius is about 10-14nm.
4. according to claim 2 or 3 described a kind of preparation methods with the process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst, it is characterized in that: the precursor of rare earth oxide is nitrate, the acetate of nitrate, acetate or their mixtures of single light rare earth La, Ce, Pr, Nd, Sm.
5. according to the described a kind of preparation method with the process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst of claim 4, it is characterized in that: soluble rare-earth salt can be coated with and be loaded in δ-Al
2O
3, θ-Al
2O
3, or δ-, on θ-mixing phase alumina, become rare earth oxide at about 500-1000 ℃ temperature lower calcination then; Also can be coated with and be loaded in γ-Al
2O
3On, when the alumina high temperature phase inversion, become rare earth oxide then.
6. according to claim 2 or 3 described a kind of preparation methods with the process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst, it is characterized in that: with high and low high temperature infusion process and the room temperature infusion process of being divided into of maceration extract temperature, the dip temperature of high temperature method is 50-98 ℃; The dip temperature of room temperature infusion process is 10-35 ℃.
7. according to claim 2 or 3 described a kind of preparation methods with the process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst, it is characterized in that: carrier carries palladium can adopt disposable dipping, also can adopt repeatedly the method for dipping to carry out, when adopting the high temperature infusion process, should use the repeatedly method of dipping.
8. according to claim 2 or 3 described a kind of preparation methods with the process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst, it is characterized in that: catalyst can or use other reducing agent water reduction with the hydrogen vapour phase reduction, when catalyst adopts the water reduction, the available hydrazine aqueous solution or with alkaline formaldehyde solution as reducing agent.
9. according to the described a kind of preparation method of claim 2 with the process for prepairng hydrogen peroxide by anthraquinone load type palladium catalyst, it is characterized in that: the preparation process final step is a catalyst with hydrogen-containing gas or hydrazine hydrate aqueous solution or alkaline formaldehyde solution reduction, during with hydrazine hydrate or alkaline formaldehyde solution reduction, follow-up washing step must be arranged, and is 7 until the pH of wash water value.
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