CN103769103A - Supported nickel catalyst for production of hydrogen peroxide through anthraquinone hydrogenation method, and preparation method thereof - Google Patents
Supported nickel catalyst for production of hydrogen peroxide through anthraquinone hydrogenation method, and preparation method thereof Download PDFInfo
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- CN103769103A CN103769103A CN201210394067.9A CN201210394067A CN103769103A CN 103769103 A CN103769103 A CN 103769103A CN 201210394067 A CN201210394067 A CN 201210394067A CN 103769103 A CN103769103 A CN 103769103A
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Abstract
The invention discloses a preparation method of a supported nickel catalyst. The method comprises the following steps: making a mixed solution containing soluble nickel salt and aluminium nitrate or a mixed solution containing soluble nickel salt, magnesium nitrate, and aluminium nitrate react with a precipitant so as to obtain a green precipitate, washing the precipitate with distilled water, then carrying out a supercritical drying treatment or an azeotropic distillation drying treatment so as to obtain a precursor of the supported nickel catalyst; calcining the precursor for 2 to 5 hours in the atmosphere of N2 and at a temperature of 200 to 600 DEG C; and then switching to an atmosphere of H2 to carry out reduction reactions for 2 to 4 hours at a temperature of 300 to 550 DEG C so as to obtain the supported high active nickel catalyst. The supported nickel catalyst has a specific surface area of 250 to 450 m<2>/g, an average pore diameter of 9 to 30 nm, and a pore volume of 1.0 to 1.9 cm<3>/g. The surface area of the active metal nickel loaded on the catalyst is 40 to 70 m<2>/g. The supported nickel catalyst is applied to the hydrogen peroxide production through an anthraquinone hydrogenation method.
Description
Technical field
The present invention relates to the preparation method of Supported Raney nickel, this Raney nickel is prepared hydrogen peroxide for anthraquinone hydrogenation.
Background technology
Hydrogen peroxide is a kind of important inorganic chemical product, is widely used in fields such as papermaking, chemical industry, food, environmental protection.The end product decomposing in hydrogen peroxide use procedure is mainly water, can not produce secondary pollution, is a kind of eco-friendly oxidant, and oxidizing process take hydrogen peroxide as oxidant has reaction condition gentleness, selective high feature.Along with the development of Green Chemical Engineering Process, hydrogen peroxide will be increasingly extensive as the application of Green Oxidant, if the emerging cleaner production processes such as cyclohexanone, caprolactam, hydroquinones, expoxy propane are all using hydrogen peroxide as oxidant.In recent years, along with some new application of hydrogen peroxide and from environmental angle, the demand of hydrogen peroxide increases day by day, and then promotes hydrogen peroxide output to keep sustainable growth situation.
The method of preparing hydrogen peroxide mainly contains isopropanol oxidation method, electrolysis and anthraquinone.Isopropanol oxidation method produces with the acetone of amount in obtaining hydrogen peroxide to be needed to process, and the hydrogen peroxide of production is more difficult separating-purifying also; Although the hydrogen peroxide product quality that electrolysis prepares is high, need to consume a large amount of electric power, cost is higher, and is unfavorable for being progressively eliminated large-scale production; Anthraquinonely have that the automation of being easy to, production capacity are large, cost and the plurality of advantages such as energy consumption is low, become the first-selection in hydrogen peroxide preparation.The anthraquinone technique of preparing hydrogen peroxide is mainly made up of the following steps: first by the anthraquinone of certain form (as 2-EAQ, EAQ) be dissolved in specific solvent and form working solution, the anthraquinone being dissolved in solvent obtains hydrogen anthraquinone (HEAQ) under the existence of hydrogenation catalyst; Obtain hydrogen peroxide to passing into oxygen-containing gas in the working solution after hydrogenation, hydrogen anthraquinone changes back to again anthraquinone simultaneously; The hydrogen peroxide generating is through extraction, purification, concentrated getting product; Working solution recycles after regenerating, dewater and purifying.But HEAQ, under the condition of hydrogen and hydrogenation catalyst, benzene ring hydrogenation can further occur, form hydrogenation tetrahydro-anthraquinone (H
4hEAQ).H
4in HEAQ, pass into oxygen and can generate hydrogen peroxide, simultaneously H
4hEAQ changes tetrahydro-anthraquinone (H into
4eAQ); H
4eAQ is the same with EAQ, can be reduced into H
4hEAQ, i.e. H
4eAQ also can participate in redox cycle reaction, and in cyclic process, produces hydrogen peroxide.But H
4the formation of EAQ can cause raw material H
2unnecessary consumption; And H
4the solubility of EAQ in solvent is lower than EAQ, H
4the a large amount of formation of EAQ in solution can cause solution viscosity to become large, even separate out solid; Meanwhile, H
4the oxidation rate of HEAQ is slower than HEAQ, and all of these factors taken together all will cause the reduction of hydrogen peroxide production capacity and the raising of cost, therefore will control H as far as possible
4the generation of EAQ.In addition, H
4under hydrogenation catalyst exists, can further there is benzene ring hydrogenation and generate hydrogenation octahydro anthraquinone (H in HEAQ
8hEAQ); Can there is hydrogenolysis and generate anthrone and anthrene in HEAQ.Once all these materials generate, and just cannot recycle formation hydrogen peroxide, are therefore referred to as catabolite.In order to improve the yield of hydrogen peroxide, the formation of necessary control degradation product.Prepare in hydrogen peroxide process anthraquinone, anthraquinone hydrogenation is crucial step, and it,, by being related to yield and the production cost of last hydrogen peroxide, is further decided by adopted hydrogenation catalyst again, the features such as outstanding catalyst must possess high activity, high selectivity, longer service life.
Anthraquinone hydrogenation process used catalyst is divided into Raney nickel and palladium catalyst.Raney's nickel is owing to producing a large amount of spent lyes in its preparation process, and anthraquinone hydrogenation device complex structure, re-uses hardly.It was once the anthraquinone main flow of preparing hydrogen peroxide as catalyst, but hydrogenation selectivity is poor, thereby had caused the unnecessary consumption of a large amount of anthraquinones and hydrogen, had increased the cost of hydrogen peroxide.Therefore in operating process in order to reduce the loss of anthraquinone, generally the degree of hydrogenation of anthraquinone is controlled at below 70%, this directly has influence on again the production efficiency of hydrogen peroxide.Palladium catalyst shows good selective in anthraquinone hydrogenation, and technological process is short while using palladium catalyst, and hydrogenation equipment is simple, easy to operate.United States Patent (USP) 2657980, discloses one palladium compound has been loaded on to γ-Al
2o
3upper, then the preparation method who reduces with hydrogen or formaldehyde, but catalytic activity is not high.Chinese patent CN1562466A discloses a kind of catalyst, improves carrier surface character by alkali metal, alkaline-earth metal and transition metal, and noble-metal-supported content, at 0.2～0.4wt%, increases the activity and selectivity of catalyst in hydrogenation process.In addition, modify by the surface to carrier, the physical property structural parameters and the Acidity of Aikalinity of carrier surface etc. that improve carrier improve activity and the stability of hydrogenation catalyst.But, make catalyst with palladium, in anthraquinone, the hydrogenation of phenyl ring starts just to carry out in reaction thereupon, although the generation of a small amount of tetrahydro-anthraquinone there is no impact to the yield of hydrogen peroxide, and also likely increases reaction rate, along with the carrying out of reaction, the gathering of tetrahydro-anthraquinone is more and more, make the retrogradation of working solution viscosity, unfavorable operation, causes hydrogen unnecessary consumption.In addition, also to make this legal system obtain the production cost of hydrogen peroxide higher for palladium catalyst fancy price.Support Raney nickel and there is low price, active advantages of higher.In order to reduce Hydrogen Vapor Pressure, reduce energy consumption, need to improve the activity of catalyst.And suitable carrier hole structure, surface acid alkalescence and higher specific area are conducive to load and the dispersion of noble metal active component, thus hydrogenation activity and the stability of raising catalyst.
Summary of the invention
Main purpose of the present invention is to provide a kind of novel Supported Raney nickel, with Al
2o
3or the MgAlO preparation method who supports Raney nickel that is carrier, wherein use overcritical or azeotropic distillation drying catalyst, can reduce surface tension, make catalyst in dry run, still can keep higher surface area, improve the decentralization of metallic nickel.This catalyst, for hydrogen dioxide solution production by anthraquinone process technique, can improve hydrogenation efficiency, and catalyst cost is low.
Technical scheme of the present invention is as follows:
A kind of preparation method of Supported Raney nickel, the method is used the mixed solution that contains soluble nickel salt and aluminum nitrate or the one in the mixed solution that contains soluble nickel salt, magnesium nitrate and aluminum nitrate to react with precipitating reagent and obtains green precipitate, gained precipitation is after distilled water washing, use supercritical drying or azeotropic distillation drying to obtain supported nickel catalyst presoma, through roasting and reduction, obtain loaded high activity metal Raney nickel again.The catalyst that this invention makes, can be used for catalysis anthraquinone hydrogenation and prepares hydrogen peroxide.
Above-mentioned preparation method, described soluble nickel salt is Ni (NO
3)
2, NiSO
4, NiCl
2or Ni (CH
3cOO)
2in one, the active component nickel loading of prepared Raney nickel is 30～80wt%.
Above-mentioned preparation method, described soluble nickel salt and the mixed solution of aluminum nitrate are by soluble nickel salt and Al (NO
3)
3.9H
2the water-soluble preparation of O, Ni in gained solution
2+with Al
3+the ratio of amount of substance be 1: 4～5: 1, Ni
2+with Al
3+total concentration is 0.1～1mol/L.
Above-mentioned preparation method, the mixed solution of described soluble nickel salt, magnesium nitrate and aluminum nitrate is by soluble nickel salt, Mg (NO
3)
2.6H
2o and Al (NO
3)
3.9H
2the water-soluble preparation of O, Ni in gained solution
2+with Mg
2+the ratio of amount of substance be 1: 4～2: 3, Ni
2+with Al
3+the ratio of amount of substance be 2: 3～13: 1, Ni
2+, Al
3+and Mg
2+total concentration is 0.1～1mol/L.
Above-mentioned preparation method, described precipitating reagent is the one in sodium carbonate or sodium bicarbonate aqueous solution, concentration is 0.1～1mol/L, precipitating reagent amount ratio stoichiometry excessive 10%～30%.
Above-mentioned preparation method, described supercritical drying drying method is: precipitation is added in autoclave, then add the absolute ethyl alcohol of 5～20 times of amounts of precipitation quality as supercritical solvent, logical N
2purge autoclave 30 minutes, with the air in the system of removing, sealing autoclave, is raised to 260 ℃ by autoclave temp, and still internal pressure reaches about 7MPa, keeps this state 1h, and then, pressure release, to normal pressure, is after this used N
2purge autoclave 2h and be down to room temperature, open seal cover and take out product, obtain supported nickel catalyst presoma.
Above-mentioned preparation method, described azeotropic distillation drying method is: precipitation wash with water after, then with absolute ethanol washing once, after filtration, then add the organic solvent that precipitates 5～50 times of amounts of quality, after stirring, 60～100 ℃ of heating solvent evaporated, obtain the presoma of supported nickel catalyst.
Above-mentioned preparation method, described organic solvent is ethanol, acetone, isopropyl alcohol, n-butanol, n-amyl alcohol or cyclohexane.
Above-mentioned preparation method, roasting and the reducing condition of described supported nickel catalyst presoma are: first at N
2under atmosphere, in 200～600 ℃ of roasting 2～5h, then switch to H
2atmosphere, at 300～550 ℃ of reductase 12～4h, obtains the loaded high activity metal Raney nickel of the present invention.
The surface area of gained catalyst of the present invention is 250～450m
2/ g, average pore size is 9～30nm, pore volume 1.0～1.9cm
3/ g.Surface area and pore-size distribution use N
2under liquid nitrogen temperature, measure adsorption-desorption thermoisopleth, then calculate by BET and BJH formula.The active metal nickel surface area of gained catalyst is 40～70m
2/ g.In catalyst, the surface area of active metal nickel passes through H
2absorption method titration obtains.Before titration, catalyst is through 400 ℃ of hydrogen reducing 2h, H
2absorption is at room temperature measured, and obtains adsorption isotherm, i.e. H
2adsorbance is with H
2the curve that pressure changes.
The novel supported nickel catalyst that the present invention makes, can be used for anthraquinone hydrogenation prepares in hydrogen peroxide reaction, its method is: take a certain amount of catalyst and be loaded in fixed bed reactors, first use the air in nitrogen replacement reaction unit, use again hydrogen exchange nitrogen at least 3 times, and then be filled with hydrogen and make the reaction pressure of fixed bed reach 0.2～0.5MPa, heating fixed bed makes reaction temperature reach 40～80 ℃.Prepare certain density working solution, carry out anthraquinone hydrogenation reaction and obtain hydrogen anthraquinone; Obtain hydrogen peroxide to passing into oxygen-containing gas in the working solution after hydrogenation again; The hydrogen peroxide generating gets product through extraction, purification; Working solution recycles after regenerating, dewater and purifying.
The specific embodiment
By following embodiment and reference example, the invention will be further described:
Embodiment 1: take 29.7g Ni (NO
3)
2.6H
2o, 27.4gAl (NO
3)
3.9H
2o and 19.2gMg (NO
3)
2.6H
2o, water-soluble, make 100ml solution; Separately get 22.9gNa
2cO
3water-soluble one-tenth 100ml solution.Under agitation above-mentioned two solution are added drop-wise to (80 ℃ of water-baths) in 200ml distilled water, generate green precipitate, precipitation is washed with distilled water, once add afterwards 100ml absolute ethyl alcohol with absolute ethanol washing again, 80 ℃ of evaporates to dryness, 120 ℃ of oven dry in baking oven, obtain green and support Raney nickel presoma.By gained Raney nickel presoma first at N
2under atmosphere, in 200 ℃ of roasting 4h, then switch to H
2atmosphere, at 400 ℃ of reductase 12 h, obtains Supported Raney nickel.Measuring its surface area is 435m
2/ g, average pore size is 9.2nm, pore volume 1.0cm
3/ g, active metal nickel surface area 44m
2/ g.
Embodiment 2: take 39.6g Ni (NO
3)
2.6H
2o and 7.35gAl (NO
3)
3.9H
2o is water-soluble, makes 100ml solution; Separately get 23.6gNa
2cO
3water-soluble one-tenth 100ml solution.Under agitation above-mentioned two solution are added drop-wise to (60 ℃ of water-baths) in 200ml distilled water, generate green precipitate, precipitation is washed with distilled water, once add afterwards 100ml n-amyl alcohol with acetone washing again, 80 ℃ of evaporates to dryness, 120 ℃ of oven dry in baking oven, obtain green and support Raney nickel presoma.By gained Raney nickel presoma first at N
2under atmosphere, in 400 ℃ of roasting 4h, then switch to H
2atmosphere, at 400 ℃ of reductase 12 h, obtains Supported Raney nickel.Measuring its surface area is 380m
2/ g, average pore size is 15nm, pore volume 1.4cm
3/ g, active metal nickel surface area 68m
2/ g.
Embodiment 3: take 34.7g Ni (NO
3)
2.6H
2o and 7.35gAl (NO
3)
3.9H
2o is water-soluble, makes 100ml solution; Separately get 23.6gNa
2cO
3water-soluble one-tenth 100ml solution.Under agitation above-mentioned two solution are added drop-wise to (60 ℃ of water-baths) in 200ml distilled water, generate green precipitate, precipitation is washed with distilled water, once add afterwards 100ml n-amyl alcohol with acetone washing again, 80 ℃ of evaporates to dryness, 120 ℃ of oven dry in baking oven, obtain green and support Raney nickel presoma.By gained Raney nickel presoma first at N
2under atmosphere, in 400 ℃ of roasting 4h, then switch to H
2atmosphere, at 400 ℃ of reductase 12 h, obtains Supported Raney nickel.Measuring its surface area is 260m
2/ g, average pore size is 29nm, pore volume 1.9cm
3/ g, active metal nickel surface area 54m
2/ g.
Embodiment 4: take the catalyst 1g of preparation in embodiment 1, be loaded on micro fixed-bed reactor and carry out activity rating.Reaction tube is Φ 10 × 50mm, and working solution effective anthraquinone concentration is 100g/L, 50 ℃ of reaction temperatures, pressure 0.3MPa, liquid air speed 12h
-1, hydrogen air speed 40ml/min.After collecting hydride, obtain product hydrogen peroxide through oxidation, extraction.Known through Standard Potassium Permanganate Solution titration, its hydrogenation efficiency is 8.50gH
2o
2/ L.
Embodiment 5: take Kaolinite Preparation of Catalyst 1g in embodiment 2, be loaded on micro fixed-bed reactor and carry out activity rating.Reactor is Φ 10 × 50mm, and working solution effective anthraquinone concentration is 100g/L, 50 ℃ of reaction temperatures, pressure 0.3MPa, liquid air speed 12h
-1, hydrogen air speed 40ml/min.After collecting hydride, obtain product hydrogen peroxide through oxidation, extraction.Known through Standard Potassium Permanganate Solution titration, its hydrogenation efficiency is 7.56gH
2o
2/ L.
Embodiment 6: take Kaolinite Preparation of Catalyst 1g in embodiment 3, be loaded on micro fixed-bed reactor and carry out activity rating.Reactor is Φ 10 × 50mm, and working solution effective anthraquinone concentration is 100g/L, 50 ℃ of reaction temperatures, pressure 0.3MPa, liquid air speed 12h
-1, hydrogen air speed 40ml/min.After collecting hydride, obtain product hydrogen peroxide through oxidation, extraction.Known through Standard Potassium Permanganate Solution titration, its hydrogenation efficiency is 7.82gH
2o
2/ L.
Embodiment 7 (reference example): take 1g industrial catalyst 0.3%Pd/Al
2o
3, be loaded on micro fixed-bed reactor and carry out activity rating.Reactor is Φ 10 × 50mm, and working solution effective anthraquinone concentration is 100g/L, 50 ℃ of reaction temperatures, pressure 0.3MPa, liquid air speed 12h
-1, hydrogen air speed 40ml/min.After collecting hydride, obtain product hydrogen peroxide through oxidation, extraction.Known through Standard Potassium Permanganate Solution titration, its hydrogenation efficiency is 6.32gH
2o
2/ L.
Claims (10)
1. the preparation method of a Supported Raney nickel, it is characterized in that: the method is used the mixed solution that contains soluble nickel salt and aluminum nitrate or the one in the mixed solution that contains soluble nickel salt, magnesium nitrate and aluminum nitrate to react with precipitating reagent and obtains green precipitate, gained precipitation is after distilled water washing, use supercritical drying or azeotropic distillation drying to obtain supported nickel catalyst presoma, again through roasting and reduction, make Supported Raney nickel, the surface area of gained catalyst is 250～450m
2/ g, average pore size is 9～30nm, pore volume 1.0～1.9cm
3/ g, active metal nickel surface area is 40～70m
2/ g.
2. preparation method according to claim 1, is characterized in that: described soluble nickel salt is Ni (NO
3)
2, NiSO
4, NiCl
2or Ni (CH
3cOO)
2in one; The active component nickel loading of described Raney nickel is 30～80wt%.
3. preparation method according to claim 1, is characterized in that: described soluble nickel salt and the mixed solution of aluminum nitrate are by soluble nickel salt and Al (NO
3)
3.9H
2the water-soluble preparation of O, Ni in gained solution
2+with Al
3+the ratio of amount of substance be 1: 4～5: 1, Ni
2+with Al
3+total concentration is 0.1～1mol/L.
4. preparation method according to claim 1, is characterized in that: the mixed solution of described soluble nickel salt, magnesium nitrate and aluminum nitrate is by soluble nickel salt, Mg (NO
3)
2.6H
2o and Al (NO
3)
3.9H
2the water-soluble preparation of O, Ni in gained solution
2+with Mg
2+the ratio of amount of substance be 1: 4～2: 3, Ni
2+with Al
3+the ratio of amount of substance be 2: 3～13: 1, Ni
2+, Al
3+and Mg
2+total concentration is 0.1～1mol/L.
5. preparation method according to claim 1, is characterized in that: described precipitating reagent is the one in sodium carbonate or sodium bicarbonate aqueous solution, and concentration is 0.1～1mol/L, precipitating reagent amount ratio stoichiometry excessive 10%～30%.
6. preparation method according to claim 1, is characterized in that described supercritical drying drying method is: precipitation is added in autoclave, then add the absolute ethyl alcohol of 5～20 times of amounts of precipitation quality as supercritical solvent, logical N
2purge autoclave 30 minutes, with the air in the system of removing, sealing autoclave, is raised to 260 ℃ by autoclave temp, and still internal pressure reaches about 7MPa, keeps this state 1h, and then, pressure release, to normal pressure, is after this used N
2purge autoclave 2h and be down to room temperature, open seal cover and take out product, obtain supported nickel catalyst presoma.
7. preparation method according to claim 1, it is characterized in that described azeotropic distillation drying method is: after precipitation washes with water, again with absolute ethanol washing once, after filtration, add again the organic solvent of 5～50 times of amounts of precipitation quality, after stirring, 60～100 ℃ of heating solvent evaporated, obtain the presoma of supported nickel catalyst.
8. preparation method according to claim 7, is characterized in that: described organic solvent is ethanol, acetone, isopropyl alcohol, n-butanol, n-amyl alcohol or cyclohexane.
9. preparation method according to claim 1, is characterized in that roasting and the reducing condition of described supported nickel catalyst presoma is: first at N
2under atmosphere, in 200～600 ℃ of roasting 2～5h, then switch to H
2atmosphere, at 300～550 ℃ of reductase 12～4h, obtains the loaded high activity metal Raney nickel of the present invention.
10. the supported nickel catalyst that a kind of supported nickel catalyst claimed in claim 1 or the preparation method described in claim 2～9 obtain is prepared the purposes in hydrogen peroxide at anthraquinone hydrogenation, it is characterized in that: take a certain amount of catalyst and be loaded in fixed bed reactors, first use the air in nitrogen replacement reaction unit, use again hydrogen exchange nitrogen at least 3 times, and then be filled with hydrogen and make the reaction pressure of fixed bed reactors reach 0.2～0.5MPa, heating fixed bed makes reaction temperature reach 40～80 ℃, carries out anthraquinone hydrogenation reaction and obtains hydrogen anthraquinone; Obtain hydrogen peroxide to passing into oxygen-containing gas in hydrogen anthraquinone again.
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|---|---|---|---|
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|---|---|---|---|
| CN201210394067.9A CN103769103A (en) | 2012-10-17 | 2012-10-17 | Supported nickel catalyst for production of hydrogen peroxide through anthraquinone hydrogenation method, and preparation method thereof |
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Cited By (6)
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|---|---|---|---|---|
| CN107185541A (en) * | 2017-06-13 | 2017-09-22 | 中触媒新材料股份有限公司 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
| CN110813333A (en) * | 2018-08-14 | 2020-02-21 | 南京大学 | Preparation method of fuel oil hydrofining catalyst |
| CN111068787A (en) * | 2019-12-25 | 2020-04-28 | 东莞东阳光科研发有限公司 | Hydrogen peroxide hydrogenation catalyst, preparation method and application thereof |
| CN112316949A (en) * | 2020-11-05 | 2021-02-05 | 山东中科新材料研究院有限公司 | Preparation method and use method of carbon-containing supported nickel alloy catalyst |
| CN115212887A (en) * | 2022-07-05 | 2022-10-21 | 南京大学 | Preparation method of reforming catalyst with high dispersion degree of active metal components |
| WO2024093075A1 (en) * | 2022-11-05 | 2024-05-10 | 广东邦普循环科技有限公司 | Method for extracting iron from ferro-nickel alloy and preparing hydrogen peroxide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185541A (en) * | 2017-06-13 | 2017-09-22 | 中触媒新材料股份有限公司 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
| CN110813333A (en) * | 2018-08-14 | 2020-02-21 | 南京大学 | Preparation method of fuel oil hydrofining catalyst |
| CN111068787A (en) * | 2019-12-25 | 2020-04-28 | 东莞东阳光科研发有限公司 | Hydrogen peroxide hydrogenation catalyst, preparation method and application thereof |
| CN111068787B (en) * | 2019-12-25 | 2022-12-27 | 东莞东阳光科研发有限公司 | Hydrogen peroxide hydrogenation catalyst, preparation method and application thereof |
| CN112316949A (en) * | 2020-11-05 | 2021-02-05 | 山东中科新材料研究院有限公司 | Preparation method and use method of carbon-containing supported nickel alloy catalyst |
| CN115212887A (en) * | 2022-07-05 | 2022-10-21 | 南京大学 | Preparation method of reforming catalyst with high dispersion degree of active metal components |
| CN115212887B (en) * | 2022-07-05 | 2023-06-06 | 南京大学 | Preparation method of reforming catalyst with high dispersity of active metal component |
| WO2024093075A1 (en) * | 2022-11-05 | 2024-05-10 | 广东邦普循环科技有限公司 | Method for extracting iron from ferro-nickel alloy and preparing hydrogen peroxide |
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Application publication date: 20140507 |