CN101497040A - Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof - Google Patents
Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof Download PDFInfo
- Publication number
- CN101497040A CN101497040A CNA2008100103445A CN200810010344A CN101497040A CN 101497040 A CN101497040 A CN 101497040A CN A2008100103445 A CNA2008100103445 A CN A2008100103445A CN 200810010344 A CN200810010344 A CN 200810010344A CN 101497040 A CN101497040 A CN 101497040A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- integral honeycomb
- active component
- integer catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a monolithic catalyst for oxydol production and a preparation method thereof. The catalyst uses ceramic monolithic honeycomb or metal monolithic honeycomb as a substrate, one or more of Al2O3, SiO2, CaO, MgO, TiO2, ZrO2, La2O3, CeO2, Fe2O3 and Cr2O3 as a coating material, and noble metal palladium as an active component to be used in an anthraquinone hydrogenation reaction of oxydol production. The monolithic catalyst adopts a preparation method of fractional support so as to effectively control depth of impregnation of the active component. The monolithic catalyst used in the anthraquinone hydrogenation process has the advantages of high activity, good selectivity and 82.21kg (100 percent of H2O2) /m<3>cat.h of space-time yield of the oxydol, which is over 3 times more than a commercial bead catalyst.
Description
Technical field
The present invention relates to the production of hydrogen peroxide, specifically a kind of is that the hydrogen peroxide production of carrier is with catalyst and preparation method with cordierite integral honeycomb or metal integral honeycomb, oxide with main group metal, transition metal or rare earth metal is a coating material, and palladium is an active component.
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 that decomposes in the hydrogen peroxide use mainly is a water, can not produce secondary pollution, is a kind of eco-friendly oxidant, and is that the oxidizing process of oxidant has reaction condition gentleness, advantage that selectivity is high with the hydrogen peroxide.Along with the continuous development of green chemical industry process, hydrogen peroxide will be increasingly extensive as the application of green oxidation agent, as cyclohexanone, caprolactam, hydroquinones, emerging cleaner production process such as expoxy propane all with hydrogen peroxide as oxidant.In recent years, along with some new application of hydrogen peroxide and from environmental angle, the demand of hydrogen peroxide will increase day by day, and then impels hydrogen peroxide output to keep sustainable growth situation.The production capacity of external hydrogen peroxide plant in 2005 reaches 3,000,000 t/a (100%H approximately
2O
2Meter).The same development of domestic hydrogen peroxide production rapidly, production capacity and output is with annual about 15%～20% speed increase, nearly hundred covers of domestic oxydol production apparatus in the end of the year 2006, production capacity is near 1,000,000 tons of (100%H
2O
2Meter).
In hydrogen peroxide preparation technology, anthraquinone autoxidation method has overwhelming superiority, and its core process is exactly the anthraquinone catalytic hydrogenation, and hydrogenation catalyst is the key that influences hydrogenation process.Problems such as hydrogenation catalyst has experienced the evolution that Raney Raney nickel, palladium black catalyst arrive non-uniform supported palladium catalyst, still exists catalyst efficiency low at present, and inactivation is fast.The integrated catalyst that the integral honeycomb catalyst is made up of the parallel channels of many narrow proper alignment, has millimetre-sized reaction channel, characteristic size is little, also has low pressure drop, low energy consumption simultaneously, need not to carry out product and catalyst separation and is easy to plurality of advantages such as integrated amplification.For heterogeneous reaction, when the suitable gas of maintenance, liquid two-phase speed, fluid will form piston flow in the integer catalyzer passage, only exist one deck very thin liquid film between bubble and the conduit wall this moment, also exist liquid phase to circulate in the fluid column simultaneously, this will increase solution-air and liquid-solid 's mass transfer rate greatly, improve the utilization ratio of catalyst.
Akzo Nobel company is used for the anthraquinone hydrogenation process with the overall structure catalyst.At first selecting silica for use is carrier material, through after the extrusion molding, carries out sensitization with the stannous chloride aqueous solution, activates with the acid chlorization aqueous palladium.Divided for three steps carried out and carry the palladium activation: with ammonia, sal-ammoniac and palladium bichloride mixture aqueous solution dipping, to add NaH more slowly earlier
2PO
3The aqueous solution carries out acid rinsing and drying at last, finishes Preparation of catalysts.The whole process of preparation influence factor is many, complex process.Preparation method described in the Chinese patent CN1990100A is, carrier and active component together behind the ball milling, be impregnated in and make catalyst on the matrix.This preparation process must cause the part active component to be wrapped or bury, and prolongs reactant and enters the evolving path of active sites, reduces touch opportunity, and catalyst utilization is low
Summary of the invention
The object of the present invention is to provide a kind of integer catalyzer and preparation and application that hydrogen peroxide is produced that be used for.It uses integral honeycomb as matrix, the method that adopts substep to support height ratio top coat and active component prepares catalyst, effectively control activity component impregnation thickness by adjusting the coating amount, thereby reduce the inner resistance to mass tranfer of catalyst, improve activity of such catalysts and selectivity.The integral catalyzer of preparation is used for the anthraquinone hydrogenation process, and activity is high, selectivity is good.
For achieving the above object, the technical solution used in the present invention is:
The integral honeycomb catalyst that is used for the anthraquinone hydrogenation producing hydrogen peroxide provided by the invention, it is made up of integral honeycomb matrix, coating material and active component; It is matrix with the integral honeycomb, adopts the dipping that distributes to support, and at first floods Al on the surface of integral honeycomb
2O
3, SiO
2, CaO, MgO, TiO
2, ZrO
2, La
2O
3, CeO
2, Fe
2O
3, Cr
2O
3In a kind of or two kinds be whole basal body coating layer material, its weight is the 5-60% of honeycomb substrate, palladium-impregnated active component layer on the coating material layer then, its load capacity is 0.01～2wt% of honeycomb substrate and coating material gross weight
The thickness 5-100 μ m of described coating material layer, active component layer thickness 1-100 μ m; Described integral honeycomb is cordierite integral honeycomb or FeCrAl metal integral honeycomb, and its duct opening includes but not limited to circle, square or triangle etc.; Cellular set body opening density is 50-900cpsi (hole/square inch), is preferably 100-600cpsi.
The preparation process of described integer catalyzer is:
1) preliminary treatment of cordierite integral honeycomb matrix: with volumetric concentration is the rare HNO of 3-15%
3Soaked 2-12 hour, deionized water is washed till neutrality, 120 ℃ dry 2-6 hour, 1000 ℃ roasting 2-10 hour;
2) choose one or both materials in nitrate, hydroxide and/or the oxide of Al, Si, Ca, Mg, Ti, Zr, La, Ce, Fe and Cr metal, adding mass concentration is 1-10% nitric acid, every gram material added the rare nitric acid of 3-5ml, through 6-18 hour ball milling form slurry;
Or one or both soluble-salts (as nitrate, hydroxide or oxide) of Al, Si, Ca, Mg, Ti, Zr, La, Ce, Fe and Cr metal are made colloidal sol with sol-gal process, concentration is 0.8-1.2mol/L;
3) with above-mentioned steps 2) slurry that obtained or sol impregnation on the integral honeycomb matrix of handling through step 1), form the carrier of band coating after dry, the 350-1200 ℃ roasting;
4) with 3) described integral honeycomb carrier impregnation is in the precursor solution that contains Pd, can carry out the single or multiple dipping, at every turn all through super-dry, 200-800 ℃ roasting, forms catalyst.
Described step 3) is with above-mentioned steps 2) slurry that obtained or sol impregnation can adopt once on the integral honeycomb matrix of handling through step 1) or flood once more than and support, flood all through super-dry, roasting process at every turn.
The predecessor of described active component Pd is preferably palladium bichloride, palladium nitrate or palladium sponge, preferred palladium bichloride; Precursor solution pH=3, mass concentration is 5～100mg/ml.
The drying of described coating and active component was selected for use microwave drying 1-30 minute or freeze drying 2-6 hour;
The sintering temperature of described coated carrier is preferably 650-1100 ℃, roasting time 2-4 hour; The active component sintering temperature is preferably 500 ℃, roasting time 2 hours.
The predecessor of coating material of the present invention can be one or more mixing of oxide, hydroxide, nitrate or chloride, oxychlorination thing etc.
Described integer catalyzer can be used in the reaction of anthraquinone hydrogenation producing hydrogen peroxide.
The present invention has following advantage:
1. the integer catalyzer activity component impregnation degree of depth of the present invention can be controlled by adjusting the coating amount, activity component load quantity and activity component impregnation layer depth match, improve the mass-transfer efficiency of reaction mass between gas-liquid, liquid-solid and gas-solid, reduced inner resistance to mass tranfer.
2. the present invention proposes a kind of preparation method of integer catalyzer, and is used for anthraquinone catalytic hydrogenation producing hydrogen peroxide process.50 ℃ of reaction temperatures, pressure 0.3MPa, liquid air speed 12h
-1, gas space velocity 120h
-1Under the condition, space-time yield 20.93～82.21kg.H
2O
2(100%)/m
3.cat.h, be more than 3 times of commercial beaded catalyst.
3. integer catalyzer of the present invention is compared with traditional anthraquinone hydrogenation beaded catalyst, has overcome problems such as loss of active component, wearing and tearing, and need not to carry out separating of reactant liquor and catalyst, and filling and replacing convenient catalyst are quick.
The specific embodiment
Embodiment 1:
The coating paste preparation
Take by weighing 4.3gAl
2O
33H
2O, 5.5gAl (OH)
3, 6.4g γ-Al
2O
3, 3.0gAl (NO
3)
3And the 60ml mass concentration is 10%HNO
3Solution, ball milling obtain pulpous state suspension after 18 hours.
Preparation of Catalyst
With 400cpsi cordierite integral honeycomb matrix volumetric concentration is 3% rare HNO
3Handle, deionized water washed back 120 ℃ of dryings 2 hours, after 1000 ℃ of high temperature were handled in 2 hours, the above-mentioned mass concentration of excessive dipping is 20% pulpous state suspension, microwave drying 10min, 850 ℃ of roastings 2 hours, repeatedly the back coating supports the 38wt% that weight is honeycomb substrate behind the impregnation-calcination.Flooding concentration subsequently is the PdCl3 solution of 20mg/ml, and behind the microwave drying 5min, 500 ℃ of roastings 2 hours obtain 0.6wt%Pd/Al
2O
3/ Monolith catalyst A, impregnate layer thickness 35 μ m.
Evaluating catalyst
Integer catalyzer anthraquinone catalytic hydrogenation reaction carries out in fixed bed reactors.The 8ml catalyst of packing into is used H before the reaction
2Reduction, 50 ℃ of reduction temperatures, H
2Flow rate 20ml/min, the recovery time is 3 hours.Reduction finishes the back and feeds working solution, and working solution consists of: every liter of solution (heavy aromatics 750ml, trioctyl phosphate 250ml) dissolving 130 gram 2-EAQs, flow is 10ml/min, H
2Flow 100ml/min, hydrogenation temperature 50, pressure 0.3MPa.
Embodiment 2:
The coating preparation
Take by weighing metatitanic acid 12.0g, adding concentration is that 10%HCl 15ml and concentration are 10% HNO
35ml, ball milling get pulpous state suspension after 18 hours stand-by.
Catalyst preparation process is identical with embodiment 1, obtains 0.6wt%Pd/TiO
2/ Monolith catalyst B, impregnate layer 30 μ m.Appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 3:
Catalyst preparation process is as described in the embodiment 1, and sintering temperature is adjusted into 650 ℃ in the Muffle furnace, repeatedly floods active component, and drying and roastings all obtains 1.3wt%Pd/Al at every turn
2O
3/ Monolith catalyst C, impregnate layer thickness are 60 μ m.Appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 4:
Catalyst preparation process is as described in the embodiment 1, and the coated carrier sintering temperature is 900 ℃, obtains 0.6wt%Pd/Al
2O
3/ Monolith catalyst D.Appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 5:
Catalyst preparation process is as described in the embodiment 1, dipping pulpous state suspension, and after the microwave drying, sintering temperature is 1000 ℃ of roastings 2 hours in the Muffle furnace, obtains 0.6wt%Pd/Al
2O
3/ Monolith catalyst E.Appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 6:
Catalyst preparation process is as described in the embodiment 1, and the used nitric acid mass concentration of ball milling is adjusted into 5%, and amount is the 5wt% of honeycomb substrate on the coating, obtains 0.2wt%Pd/Al at last
2O
3/ Monolith catalyst F, impregnate layer thickness 8 μ m.Appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 7:
Catalyst preparation process is as described in the embodiment 6, through behind the dipping repeatedly, and drying and roasting all at every turn, amount obtains 0.6wt%Pd/Al for the 15wt% of honeycomb substrate on the coating
2O
3/ Monolith catalyst G, impregnate layer thickness 20 μ m.Appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 8:
Preparation of Catalyst is as described in the embodiment 7, and amount be the 40wt% of honeycomb substrate on the coating, the PdCl of employing 60mg/ml
2Solution repeatedly floods, and drying and roastings all obtains 1.8wt%Pd/Al at every turn
2O
3/ Monolith catalyst H, impregnate layer thickness are 90 μ m.Appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 9,10:
Catalyst preparation process is as described in the embodiment 1, and optional holes density is that 100,300 honeybees are matrix, and substrate pretreated is adjusted into 10% with the nitric acid volumetric concentration, dipping pulpous state suspension, and amount is 15wt% on the coating, obtains 0.6wt%Pd/Al
2O
3/ Monolith catalyst I, J.Appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 11:
The coating preparation
In the 400ml beaker, pour 100ml Zr (NO into
3) solution (concentration is 2mol/L), drip concentrated ammonia liquor, until Zr (NO
3) solution precipitates the formation paste fully, and then the dropping mass concentration is 5% HNO
3Solution until precipitation dissolving, stirs that solution becomes translucent after 3-4 hour, formation Zr colloidal sol stand-by (concentration 1mol/L) after the standing over night.
Take by weighing the CeO of 17.2g with the homogeneous precipitation method preparation
2Powder adds above-mentioned Zr colloidal sol 25ml and concentration and is 10% HNO
3Solution 25ml, ball milling get pulpous state suspension after 18 hours stand-by.
Preparation of catalysts:
Method for preparing catalyst according to embodiment 1, with the blank carrier impregnation after handling in above-mentioned Ce-Zr pulpous state suspension, respectively 900 ℃, 1000 ℃, 1100 ℃ following roastings 2 hours, obtaining measuring on the coating is the carrier of 30wt%, the dipping active component palladium, obtain 0.6wt%Pd/Ce-Zr/Monolith catalyst K, L, M, impregnate layer thickness is 15 μ m substantially.Appreciation condition is identical with embodiment 1.
The results are shown in Table 1.
Embodiment 12:
With the hole density of purchasing is that 400 Fe75-Cr20-Al5 metal beehive is processed into Φ 1 * 5 cylinder, the process acetone soln is after ultrasonic 10 minutes, deionized water washing air dry, high-temperature heat treatment is 10 hours in Muffle furnace, contain aluminium suspension described in the cooling back dipping embodiment 1, freeze drying 2 hours, 850 ℃ of roastings 2 hours, the concentration of flooding pH=3 again is the PdCl of 20mg/ml
2Solution, 120 ℃ of dryings 2 hours, 500 ℃ of roastings obtained 0.6%Pd/Al after 2 hours
2O
3/ Metal Monolith catalyst n, appreciation condition is identical with embodiment 1.The results are shown in Table 1.
The comparative example:
Embodiment 13:
With the HNO of 400cpsi integral honeycomb catalyst with volumetric concentration 3%
3Handle, deionized water washing back is dry, and 1000 ℃ of high temperature are after 2 hours, and direct impregnation pH=3, concentration are the PdCl of 20mg/ml
2Solution, other process is described with embodiment 1, obtains the 0.6wt%Pd/Monolith catalyst P, and appreciation condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 14:
Commercial carrying alumina palladium (0.3wt%) catalyst Q, impregnate layer thickness 50 μ m estimating with under the condition, the results are shown in Table 1.
Table 1. catalyst performance table
| Title | A | B | C | D | E | F | G | H |
| Hydrogenation efficiency g/l | 6.64 | 4.5 | 4.47 | 3.95 | 3.52 | 2.97 | 3.61 | 4.48 |
| Space-time yield kg/m 3.h | 82.21 | 50.8 | 51.39 | 48.24 | 41.15 | 37.21 | 45.41 | 55.28 |
| Title | I | J | K | L | M | N | P | Q |
| Hydrogenation efficiency g/l | 3.6 | 3.33 | 1.78 | 3.24 | 1.86 | 2.22 | 1.5 | 2.05 |
| Space-time yield kg/m 3.h | 45.17 | 48.01 | 20.93 | 37.39 | 22.80 | 22.02 | 18.6 | 25.65 |
Claims (8)
1. one kind is used for the integer catalyzer that hydrogen peroxide is produced, and it is a matrix with the integral honeycomb, it is characterized in that: adopt the dipping that distributes to support, at first flood Al on the surface of integral honeycomb
2O
3, SiO
2, CaO, MgO, TiO
2, ZrO
2, La
2O
3, CeO
2, Fe
2O
3, Cr
2O
3In a kind of or two kinds be whole basal body coating layer material, its weight is the 5-60% of honeycomb substrate, palladium-impregnated active component layer on the coating material layer then, its load capacity is 0.01～2wt% of honeycomb substrate and coating material gross weight.
2. according to the described integer catalyzer of claim 1, it is characterized in that: the thickness 5-100 μ m of described coating material layer, active component layer thickness 1-100 μ m.
3. according to the described integer catalyzer of claim 1, it is characterized in that: described integral honeycomb is cordierite integral honeycomb or FeCrAl metal integral honeycomb.
4. the preparation method of the described integer catalyzer of claim 1 is characterized in that:
1) preliminary treatment of cordierite integral honeycomb matrix: with volumetric concentration is the rare HNO of 3-15%
3Soaked 2-12 hour, deionized water is washed till neutrality, 120 ℃ dry 2-6 hour, 1000 ℃ roasting 2-10 hour;
2) choose one or both materials in nitrate, hydroxide and/or the oxide of Al, Si, Ca, Mg, Ti, Zr, La, Ce, Fe and Cr metal, adding mass concentration is 1-10% nitric acid, every gram material added the rare nitric acid of 3-5ml, through 6-18 hour ball milling form slurry;
Or one or both soluble-salts of Al, Si, Ca, Mg, Ti, Zr, La, Ce, Fe and Cr metal are made colloidal sol with sol-gal process, concentration is 0.8-1.2mol/L;
3) with above-mentioned steps 2) slurry that obtained or sol impregnation on the integral honeycomb matrix of handling through step 1), form the carrier of band coating after dry, the 350-1200 ℃ roasting;
4) with 3) described integral honeycomb carrier impregnation is in the precursor solution that contains Pd, can carry out the single or multiple dipping, at every turn all through super-dry, 200-800 ℃ roasting, forms catalyst.
5. according to the preparation method of the described integer catalyzer of claim 4, it is characterized in that: described step 3) is with above-mentioned steps 2) slurry that obtained or sol impregnation can adopt once on the integral honeycomb matrix of handling through step 1) or flood once more than and support, flood all through super-dry, roasting process at every turn.
6. according to the preparation method of the described integer catalyzer of claim 4, it is characterized in that: the predecessor of described active component Pd is palladium bichloride, palladium nitrate or palladium sponge; Precursor solution pH=3, mass concentration is 5～100mg/ml.
7. according to the preparation method of the described integer catalyzer of claim 4, it is characterized in that: the drying of described coating and active component was selected for use microwave drying 1-30 minute or freeze drying 2-6 hour;
The sintering temperature of described coated carrier is 650-1100 ℃, roasting time 2-4 hour; The active component sintering temperature is 500 ℃, roasting time 2 hours.
8. the application of the described integer catalyzer of claim 1 is characterized in that: described integer catalyzer is used for the reaction of anthraquinone hydrogenation producing hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100103445A CN101497040B (en) | 2008-02-03 | 2008-02-03 | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100103445A CN101497040B (en) | 2008-02-03 | 2008-02-03 | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101497040A true CN101497040A (en) | 2009-08-05 |
| CN101497040B CN101497040B (en) | 2011-05-11 |
Family
ID=40944437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100103445A Expired - Fee Related CN101497040B (en) | 2008-02-03 | 2008-02-03 | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497040B (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966454A (en) * | 2010-08-31 | 2011-02-09 | 苏州大学 | Catalyst for use in preparation of hydrogen peroxide by anthraquinone method and preparation method thereof |
| CN102389799A (en) * | 2011-09-19 | 2012-03-28 | 傅骐 | Palladium catalyst for production of H2O2 by using fixed bed anthraquinone method and preparation method thereof |
| CN102658134A (en) * | 2012-04-23 | 2012-09-12 | 陕西开达化工有限责任公司 | Doping-type Pd/aluminum oxide titanium catalyst hydrogenated through anthraquinone process and preparation method thereof |
| CN102658207A (en) * | 2012-04-23 | 2012-09-12 | 陕西开达化工有限责任公司 | High-dispersion palladium catalyst used for anthraquinone hydrogenation and preparation method of same |
| CN103769092A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst for hydrogen peroxide production through anthraquinone method and preparation method thereof |
| CN103769091A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst for hydrogen peroxide preparation through anthraquinone method and preparation method thereof |
| CN103769093A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst and preparation method thereof |
| CN104368336A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | Monolithic catalyst for hydrogen peroxide production through pentylanthraquinone process and preparation method thereof |
| CN104368374A (en) * | 2014-09-24 | 2015-02-25 | 中国科学院大连化学物理研究所 | High-dispersion monolithic catalyst for hydrogen peroxide synthesis, and preparation method and application thereof |
| CN105268433A (en) * | 2014-06-13 | 2016-01-27 | 中国科学院大连化学物理研究所 | Highly-dispersed catalyst for hydrogen peroxide synthesis and preparation method thereof |
| CN105536778A (en) * | 2015-12-11 | 2016-05-04 | 北京化工大学 | Monolithic catalyst for hydrogenation process of anthraquinone-process preparation of hydrogen peroxide and preparation method thereof |
| CN106669665A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Integral catalyst for hydrogen peroxide production process through anthraquinone process and preparation method of integral catalyst |
| WO2017128946A1 (en) * | 2016-01-27 | 2017-08-03 | 中国科学院大连化学物理研究所 | Highly-dispersed particulate catalyst for use in hydrogen peroxide synthesis, preparation method therefor and application thereof |
| CN107055481A (en) * | 2016-10-18 | 2017-08-18 | 上海睿思化工科技有限公司 | A kind of preparation method of hydrogen peroxide |
| CN107694562A (en) * | 2016-08-08 | 2018-02-16 | 中国科学院大连化学物理研究所 | A kind of integer catalyzer and its preparation and application |
| CN107777670A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method for hydrogenation of hydrogen dioxide solution production by anthraquinone process |
| CN109745990A (en) * | 2017-11-02 | 2019-05-14 | 中国石油化工股份有限公司 | oxychlorination catalyst and its preparation method and application |
| CN109745989A (en) * | 2017-11-02 | 2019-05-14 | 中国石油化工股份有限公司 | oxychlorination catalyst and its preparation method and application |
| CN110302781A (en) * | 2019-06-14 | 2019-10-08 | 东莞东阳光科研发有限公司 | A kind of catalyst and preparation method thereof |
| CN111841565A (en) * | 2020-07-28 | 2020-10-30 | 湖南艾凯环保科技有限公司 | Normal-temperature ozone-removing catalytic material |
| WO2020256328A1 (en) * | 2019-06-21 | 2020-12-24 | 희성촉매 주식회사 | Catalyst for synthesis of hydrogen peroxide and recovery, and method of preparing same |
| CN114130390A (en) * | 2021-10-20 | 2022-03-04 | 四川大学 | Method for preparing integral torch combustion catalyst based on etching method and application |
| WO2022103150A1 (en) * | 2020-11-16 | 2022-05-19 | 희성촉매 주식회사 | Catalyst for regenerating working solution for synthesizing hydrogen peroxide |
| WO2022119192A1 (en) * | 2020-12-04 | 2022-06-09 | 희성촉매 주식회사 | Catalyst for hydrogen peroxide synthesis and regeneration |
| CN115445621A (en) * | 2022-08-26 | 2022-12-09 | 中触媒新材料股份有限公司 | Preparation method and application of nickel-based catalyst for producing hydrogen peroxide by anthraquinone process |
| CN117427633A (en) * | 2023-09-12 | 2024-01-23 | 陕西开达化工有限责任公司 | Novel efficient catalyst in technology for producing hydrogen peroxide by anthraquinone process and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175931C (en) * | 2003-02-21 | 2004-11-17 | 福州大学 | Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof |
| CN1990100B (en) * | 2005-12-27 | 2010-05-12 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst |
-
2008
- 2008-02-03 CN CN2008100103445A patent/CN101497040B/en not_active Expired - Fee Related
Cited By (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966454A (en) * | 2010-08-31 | 2011-02-09 | 苏州大学 | Catalyst for use in preparation of hydrogen peroxide by anthraquinone method and preparation method thereof |
| CN102389799A (en) * | 2011-09-19 | 2012-03-28 | 傅骐 | Palladium catalyst for production of H2O2 by using fixed bed anthraquinone method and preparation method thereof |
| CN102389799B (en) * | 2011-09-19 | 2012-11-14 | 傅骐 | Palladium catalyst for production of H2O2 by using fixed bed anthraquinone method and preparation method thereof |
| CN102658134A (en) * | 2012-04-23 | 2012-09-12 | 陕西开达化工有限责任公司 | Doping-type Pd/aluminum oxide titanium catalyst hydrogenated through anthraquinone process and preparation method thereof |
| CN102658207A (en) * | 2012-04-23 | 2012-09-12 | 陕西开达化工有限责任公司 | High-dispersion palladium catalyst used for anthraquinone hydrogenation and preparation method of same |
| CN103769091B (en) * | 2012-10-24 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of anthraquinone hydrogenation catalyst preparing hydrogen peroxide and preparation method thereof |
| CN103769093A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst and preparation method thereof |
| CN103769093B (en) * | 2012-10-24 | 2015-08-12 | 中国石油化工股份有限公司 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
| CN103769092B (en) * | 2012-10-24 | 2015-08-12 | 中国石油化工股份有限公司 | Hydrogenation catalyst of a kind of hydrogen dioxide solution production by anthraquinone process and preparation method thereof |
| CN103769092A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst for hydrogen peroxide production through anthraquinone method and preparation method thereof |
| CN103769091A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst for hydrogen peroxide preparation through anthraquinone method and preparation method thereof |
| CN104368336A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | Monolithic catalyst for hydrogen peroxide production through pentylanthraquinone process and preparation method thereof |
| CN105268433A (en) * | 2014-06-13 | 2016-01-27 | 中国科学院大连化学物理研究所 | Highly-dispersed catalyst for hydrogen peroxide synthesis and preparation method thereof |
| CN104368374A (en) * | 2014-09-24 | 2015-02-25 | 中国科学院大连化学物理研究所 | High-dispersion monolithic catalyst for hydrogen peroxide synthesis, and preparation method and application thereof |
| CN104368374B (en) * | 2014-09-24 | 2016-08-17 | 中国科学院大连化学物理研究所 | A kind of high dispersive integer catalyzer for hydrogen peroxide synthesis and its preparation method and application |
| CN106669665B (en) * | 2015-11-11 | 2019-03-19 | 中国石油化工股份有限公司 | The integral catalyzer and preparation method thereof of hydrogen dioxide solution production by anthraquinone process process |
| CN106669665A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Integral catalyst for hydrogen peroxide production process through anthraquinone process and preparation method of integral catalyst |
| CN105536778A (en) * | 2015-12-11 | 2016-05-04 | 北京化工大学 | Monolithic catalyst for hydrogenation process of anthraquinone-process preparation of hydrogen peroxide and preparation method thereof |
| WO2017128946A1 (en) * | 2016-01-27 | 2017-08-03 | 中国科学院大连化学物理研究所 | Highly-dispersed particulate catalyst for use in hydrogen peroxide synthesis, preparation method therefor and application thereof |
| CN107694562A (en) * | 2016-08-08 | 2018-02-16 | 中国科学院大连化学物理研究所 | A kind of integer catalyzer and its preparation and application |
| CN107694562B (en) * | 2016-08-08 | 2020-06-23 | 中国科学院大连化学物理研究所 | Monolithic catalyst and preparation and application thereof |
| CN107777670A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method for hydrogenation of hydrogen dioxide solution production by anthraquinone process |
| CN107777670B (en) * | 2016-08-31 | 2020-03-17 | 中国石油化工股份有限公司 | Hydrogenation method for producing hydrogen peroxide by anthraquinone process |
| CN107055481A (en) * | 2016-10-18 | 2017-08-18 | 上海睿思化工科技有限公司 | A kind of preparation method of hydrogen peroxide |
| CN109745990A (en) * | 2017-11-02 | 2019-05-14 | 中国石油化工股份有限公司 | oxychlorination catalyst and its preparation method and application |
| CN109745989A (en) * | 2017-11-02 | 2019-05-14 | 中国石油化工股份有限公司 | oxychlorination catalyst and its preparation method and application |
| CN110302781A (en) * | 2019-06-14 | 2019-10-08 | 东莞东阳光科研发有限公司 | A kind of catalyst and preparation method thereof |
| CN110302781B (en) * | 2019-06-14 | 2022-04-26 | 东莞东阳光科研发有限公司 | Catalyst and preparation method thereof |
| KR20200145337A (en) * | 2019-06-21 | 2020-12-30 | 희성촉매 주식회사 | A catalyst for preparing H2O2 and regenerating working solution and a method therefor |
| JP7336539B2 (en) | 2019-06-21 | 2023-08-31 | ヒソン カタリスツ コーポレイション | Hydrogen peroxide synthesis and regenerated catalyst, and method for producing the same |
| KR102220225B1 (en) * | 2019-06-21 | 2021-02-24 | 희성촉매 주식회사 | A catalyst for preparing H2O2 and regenerating working solution and a method therefor |
| CN113950371A (en) * | 2019-06-21 | 2022-01-18 | 喜星触媒株式会社 | Hydrogen peroxide synthesis and regeneration catalyst and method for producing same |
| WO2020256328A1 (en) * | 2019-06-21 | 2020-12-24 | 희성촉매 주식회사 | Catalyst for synthesis of hydrogen peroxide and recovery, and method of preparing same |
| JP2022535021A (en) * | 2019-06-21 | 2022-08-04 | ヒソン カタリスツ コーポレイション | Hydrogen peroxide synthesis and regenerated catalyst, and method for producing the same |
| CN113950371B (en) * | 2019-06-21 | 2023-12-29 | 喜星触媒株式会社 | Catalyst for synthesizing hydrogen peroxide and regenerating and its preparing process |
| CN111841565A (en) * | 2020-07-28 | 2020-10-30 | 湖南艾凯环保科技有限公司 | Normal-temperature ozone-removing catalytic material |
| WO2022103150A1 (en) * | 2020-11-16 | 2022-05-19 | 희성촉매 주식회사 | Catalyst for regenerating working solution for synthesizing hydrogen peroxide |
| WO2022119192A1 (en) * | 2020-12-04 | 2022-06-09 | 희성촉매 주식회사 | Catalyst for hydrogen peroxide synthesis and regeneration |
| KR20220078821A (en) * | 2020-12-04 | 2022-06-13 | 희성촉매 주식회사 | A catalyst for preparing H2O2 and regenerating working solution |
| KR102523337B1 (en) | 2020-12-04 | 2023-04-18 | 희성촉매 주식회사 | A catalyst for preparing H2O2 and regenerating working solution |
| CN114130390A (en) * | 2021-10-20 | 2022-03-04 | 四川大学 | Method for preparing integral torch combustion catalyst based on etching method and application |
| CN115445621B (en) * | 2022-08-26 | 2023-08-22 | 中触媒新材料股份有限公司 | Preparation method and application of nickel-based catalyst for producing hydrogen peroxide by anthraquinone process |
| CN115445621A (en) * | 2022-08-26 | 2022-12-09 | 中触媒新材料股份有限公司 | Preparation method and application of nickel-based catalyst for producing hydrogen peroxide by anthraquinone process |
| CN117427633A (en) * | 2023-09-12 | 2024-01-23 | 陕西开达化工有限责任公司 | Novel efficient catalyst in technology for producing hydrogen peroxide by anthraquinone process and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101497040B (en) | 2011-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101497040B (en) | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof | |
| CN101851160B (en) | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst | |
| CN101850273B (en) | Structured catalyst for synthesizing oxalate by CO gaseous-phase coupling and preparation method thereof | |
| CN101428216B (en) | Layered composite carrier for producing shell shaped catalyst | |
| CN102039205B (en) | Monolithic nitrogen oxide selective reduction catalyst and preparation method thereof | |
| CN101269326A (en) | Integral catalyst for producing cyclohexene with benzene hydrogenation and method for producing the same | |
| CN104084198A (en) | Platinum aluminium oxide series catalyst for preparing propylene by propane dehydrogenation and preparation method of catalyst | |
| CN109201059A (en) | A kind of dimethyl oxalate selective hydrogenation methyl glycollate catalyst and its preparation method and application | |
| CN109833901A (en) | A kind of high-dispersion loading type slurry bed hydroprocessing beaded catalyst and preparation method thereof | |
| CN108187691B (en) | A kind of preparation method and applications of the filled composite structure catalyst for CO gas phase coupling synthesis of oxalate | |
| CN104226354A (en) | Catalyst for preparing isopropanol by hydrogenating acetone as well as preparation method and application thereof | |
| CN104368336A (en) | Monolithic catalyst for hydrogen peroxide production through pentylanthraquinone process and preparation method thereof | |
| CN107899619A (en) | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof | |
| CN113042044B (en) | TiO doped with ZnO 2 -SiO 2 Preparation and application of platinum catalyst as carrier | |
| CN106423159A (en) | Anti-carbon deposition aldol condensation catalyst, preparation method thereof and method for preparing methyl methacrylate by using catalyst | |
| CN102049261B (en) | Method for preparing catalyst of acrolein by propylene oxidization | |
| CN104261347A (en) | Method for producing hydrogen by hydrolyzing ammonia borane | |
| CN101602016B (en) | Lamellar composite carrier with hydrothermal stability | |
| CN105618068A (en) | Metal wall-supported type high-temperature synthetic gas methanation catalyst as well as preparation method and application thereof | |
| CN107008493A (en) | A kind of preparation method for alkene epoxidation or the titanium-containing catalyst of ketone oxamidinating | |
| CN103285906B (en) | Dehydrogenation catalyst, preparation method and application thereof, and method for preparing cyclohexanone by cyclohexanol dehydrogenation | |
| CN101385972A (en) | Metal micro-fiber loaded silver catalyst and use thereof | |
| CN101913912A (en) | Method for coating cordierite honeycomb | |
| CN103912347B (en) | General miniature gasoline engine exhaust gas catalytic converter and preparation method thereof | |
| CN101433843B (en) | Catalyst for producing hydrogen peroxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110511 Termination date: 20210203 |