CN102658134A - Doping-type Pd/aluminum oxide titanium catalyst hydrogenated through anthraquinone process and preparation method thereof - Google Patents
Doping-type Pd/aluminum oxide titanium catalyst hydrogenated through anthraquinone process and preparation method thereof Download PDFInfo
- Publication number
- CN102658134A CN102658134A CN2012101200699A CN201210120069A CN102658134A CN 102658134 A CN102658134 A CN 102658134A CN 2012101200699 A CN2012101200699 A CN 2012101200699A CN 201210120069 A CN201210120069 A CN 201210120069A CN 102658134 A CN102658134 A CN 102658134A
- Authority
- CN
- China
- Prior art keywords
- carrier
- tio
- roasting
- dry
- solution
- 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
Images
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a doping-type Pd/aluminum oxide titanium catalyst hydrogenated through an anthraquinone process, composite Al2O3-TiO2 oxides are taken as carriers; Al2O3 is taken as main active ingredients; and in the composite Al2O3-TiO2 oxides, the mass fraction of TiO2 accounts for 3 to 30 percent, and the adding amount of the oxides of barium and/or chromium is 0.5 to 15 percent of the mass of the carriers. The invention further discloses a preparation method of the doping-type Pd/aluminum oxide titanium catalyst. The preparation method comprises the steps as follows: Al2O3 carriers are prepared firstly, and then the Al2O3 carriers are soaked in tetrabutyl titanate and are dried and roasted to obtain the composite Al2O3-TiO2 oxide carriers; then the composite Al2O3-TiO2 oxide carriers are soaked, dried and roasted so as to granular spherical composite Al2O3-TiO2 carriers containing BaO; and finally, the composite carriers are added in acidic solution for soaking, are dried and roasted after being washed until Cl- is removed completely, and are reduced in hydrogen atmosphere finally to obtain the doping-type Pd/aluminum oxide titanium catalyst. The doping-type Pd/aluminum oxide titanium catalyst hydrogenated through the anthraquinone process has the advantages of high activity and high stability.
Description
Technical field
The invention belongs to the organic catalyst technical field, relate to a kind of doping type palladium/aluminium oxide titanium catalyst that is used for anthraquinone hydrogenation, the invention still further relates to this Preparation of catalysts method.
Background technology
Anthraquinone is that the world produces H at present
2O
2One of the most ripe technology.Anthraquinone technological process mainly comprises hydrogenation, oxidation and 3 processes of extraction, and wherein hydrogenation process is the core of whole technology.Research has the key technology that high activated catalyst is alkyl-anthraquinone method hydrogen peroxide manufacture field at present.And at anthraquinone production H
2O
2Hydrogenation process in, alumina load type palladium catalyst since its consumption low, active high, be prone to regeneration and advantage such as safe in utilization becomes the most frequently used hydrogenation catalyst at present.But because palladium is a noble metal, cost an arm and a leg simultaneously, avoid the generation of deep hydrogenation reaction again, active material is proposed higher requirement in the dispersion of catalyst surface and the thickness of dipping in order to guarantee hydrogenation efficiency.Except load process, the performance of carrier also directly all has material impact to intensity, specific area, the metal of catalyst at the decentralization of carrier surface and the technical indicators such as thickness of catalyst soakage.Have some researchs at present: Chinese patent " producing hydrogen peroxide by using anthraquinone method high efficiency load type bimetal catalyst " (application number 99126993.4 about the preparing carriers method of aluminium oxide and improvement thereof; Publication number CN1259483, open day on July 12nd, 2000) a kind of 950 ℃ of baked aluminium oxide or TiO are disclosed
2-Al
2O
3The preparation method of composite oxide carrier, but this carrier is mainly used in the metallic catalyst that contains platinum.Another Chinese patent " aluminum-silicon-titanium composite oxide carrier and load type catalytic hydro-dearomatization catalyst " (publication number CN101327453A, open day on December 24th, 2008) discloses a kind of Al
2O
3-SiO
2-TiO
2The preparation method of complex carrier, the metallic catalyst of this composite carrier load is platinum and palladium bimetallic, but is mainly used in the hydrogenation aromatics-removing aspect of diesel oil.
The preparation of high activity and stable metallic catalyst is inseparable with the structure control of carrier, and the catalyst that is applied to the palladium aluminium oxide at present mainly is γ-Al
2O
3, the preparation method comprises hydro-thermal method, low-temperature sintering method and expanding agent method etc.But for γ-Al
2O
3Relatively poor this problem of heat endurance effectively do not solved yet, so the intensity of catalyst is not high, and the palladium catalyst layer thickness that existing dipping method obtains is low excessively, makes catalyst activity not high.
Summary of the invention
Doping type palladium/aluminium oxide the titanium catalyst that the purpose of this invention is to provide a kind of anthraquinone hydrogenation, catalyst activity is high, and stability is high.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
The technical scheme that the present invention adopted is, the doping type palladium of anthraquinone hydrogenation/aluminium oxide titanium catalyst is made up of the oxide of carrier, main active component, barium and/or chromium, and carrier is Al
2O
3-TiO
2Composite oxides, main active component are Al
2O
3Al
2O
3-TiO
2TiO in the composite oxides
2Shared mass fraction is 3%～30%, Al
2O
3Mass fraction is 60%～95%, and all the other are impurity, and the addition of the oxide of barium and/or chromium is 0.5%～15% of a complex carrier.Specific surface area of catalyst is 65m
2/ g～300m
2/ g, pore volume are 0.35mL/g～1.0mL/g, and the aperture is at 9nm～25nm, and the palladium layer thickness is 150 ± 10 μ m, and the content of palladium is 0.2 ± 0.05wt%.
The preparation method of the doping type palladium of the anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, specifically carry out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier;
Step 2
With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 540 ℃ of roasting 2h, again in 950 ℃ of roasting 4h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier;
Step 4
The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L-8mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 3-4h, reduction 3-4h promptly gets under hydrogen atmosphere at last.
The another kind of preparation method of the doping type palladium of anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, specifically carry out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 15% ammoniacal liquor to pH value at 90 ℃ is 8.0, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 60 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier;
Step 2
With Al
2O
3Carrier is with the dilution heat of sulfuric acid dipping of titanium sulfate, and washing to solution behind the stirring 30min does not have SO
4 2-, dry 12h under 120 ℃ again in 550 ℃ of following roasting 4h, makes composite oxide carrier Al
2O
3-TiO
2
Step 3
With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 550 ℃ of roasting 2h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier;
Step 4
The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 9mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 550 ℃ of roasting 3h, reduction 3h promptly gets under hydrogen atmosphere at last.
Another preparation method of the doping type palladium of anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, specifically carry out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier;
Step 2
With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
With the composite oxide carrier Al that obtains
2O
3-TiO
2Use ZrOCl
2The saturated dipping of solution adds urea liquid behind the stirring 8h, and reaction 10h filters, washs and remove Cl under 60 ℃
-, behind 120 ℃ of dry 5h,, obtain containing ZrO again at 550 ℃ of following roasting 4h
2Graininess Al
2O
3-TiO
2Spherical complex carrier;
Step 4
To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 6mmol/L-7mmol/L
2PdCl
4Acid solution dipping, again with the deionized water of slow drip with catalyst wash to there not being Cl
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 4h, reduction 3-4h promptly gets under hydrogen atmosphere at last.
Another preparation method of the doping type palladium of anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, specifically carry out according to following steps:
Step 1
At Al (NO
3)
3In the solution, adding 10% ammonia spirit, is in the gel that this obtains, to add polyglycol solution again at 10 o'clock to pH, stirs 2h, centrifugalizes after placing 24h, and sediment in 120 ℃ of dry 2h down, then at 550 ℃ of following roasting 4h, is obtained Al
2O
3Carrier;
Step 2
With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
With composite oxide carrier Al
2O
3-TiO
2With Zr (NO
3)
4 Solution impregnation 120 ℃ of oven dry down, obtains containing ZrO behind 550 ℃ of following roasting 4h then
2Graininess Al
2O
3-TiO
2Spherical complex carrier;
Step 4
To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L-8mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 3-4h, reduction 3-4h promptly gets under hydrogen atmosphere at last.
The high degree of dispersion palladium catalyst beneficial effect that the present invention is used for anthraquinone hydrogenation is; Add the Stability Analysis of Structures additive to improve the heat endurance of carrier; Through the dipping method different the carrier that obtains is flooded simultaneously with prior art; Obtain having the doping type palladium aluminium oxide catalyst of high activity and stability, it is not high to have solved catalyst strength, and the palladium layer thickness is crossed low and problem such as catalyst activity that cause is not high.Catalyst granules intensity obviously improves, and can reach more than the 80N.And the palladium layer thickness that is fit to improves catalyst activity greatly, and the highest hydrogenation efficiency can reach 9.8gH
2O
2/ L, system's effective anthraquinone is formed stable.
Description of drawings
Fig. 1 is that the hydrogenation efficiency of catalyst anthraquinone hydrogenation is with temperature changing trend figure;
Fig. 2 is the total effective anthraquinone content of a reaction system changing trend diagram in time.
The specific embodiment
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is elaborated.
The doping type palladium of anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, carrier are Al
2O
3-TiO
2Composite oxides, main active component are Al
2O
3Al
2O
3-TiO
2TiO in the composite oxides
2Shared mass fraction is 3%～30%, Al
2O
3Mass fraction is 60%～95%, and the addition of the oxide of barium and/or chromium is 0.5%～15% of a complex carrier.Specific surface area of catalyst is 65m
2/ g～300m
2/ g, pore volume are 0.35mL/g～1.0mL/g, and the aperture is at 9nm～25nm, and the palladium layer thickness is 150 ± 10 μ m, and the content of palladium is 0.2 ± 0.05wt%.
The preparation method of the doping type palladium of anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, specifically carry out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and dripping 20% ammoniacal liquor to pH value down at 90 ℃ is 7.5, stirs 3h, filters, and spending in deionised water to the solution does not have chlorion.In filter cake, drip concentration subsequently and be 0.3% HNO
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, with this colloidal sol in 50 ℃ of dry 24h, after again at 550 ℃ of roasting 2h, obtain Al
2O
3Carrier.
Step 2
With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 540 ℃ of roasting 2h, again in 950 ℃ of roasting 4h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier.
Step 4
The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L-8mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 3-4h, it is 0.20wt%-0.23wt% that the 3-4h that under hydrogen atmosphere, reduces at last obtains palladium content, thickness is the catalyst of 150 μ m-160 μ m.
The another kind of preparation method of the doping type palladium of anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, specifically carry out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and dripping 15% ammoniacal liquor to pH value down at 90 ℃ is 8.0, stirs 3h, filters, and spending in deionised water to the solution does not have chlorion.In filter cake, drip concentration subsequently and be 0.3% HNO
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, with this colloidal sol in 60 ℃ of dry 24h, after again at 550 ℃ of roasting 2h, obtain Al
2O
3Carrier.
Step 2
With Al
2O
3Carrier is with the dilution heat of sulfuric acid dipping of titanium sulfate, and washing to solution behind the stirring 30min does not have SO
4 2-, dry 12h under 120 ℃ again in 550 ℃ of following roasting 4h, makes composite oxide carrier Al
2O
3-TiO
2
Step 3
With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 550 ℃ of roasting 2h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier.
Step 4
The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 9mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 550 ℃ of roasting 3h, it is 0.25wt% that the 3h that under hydrogen atmosphere, reduces at last obtains palladium content, thickness is the catalyst of 146 μ m.
Another preparation method of the doping type palladium of anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, specifically carry out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and dripping 20% ammoniacal liquor to pH value down at 90 ℃ is 7.5, stirs 3h, filters, and spending in deionised water to the solution does not have chlorion.In filter cake, drip concentration subsequently and be 0.3% HNO
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, with this colloidal sol in 50 ℃ of dry 24h, after again at 550 ℃ of roasting 2h, obtain Al
2O
3Carrier.
Step 2
With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
With the composite oxide carrier Al that obtains
2O
3-TiO
2Use ZrOCl
2The saturated dipping of solution adds urea liquid behind the stirring 8h, and reaction 10h filters, washs and remove Cl under 60 ℃
-, behind 120 ℃ of dry 5h,, obtain containing ZrO again at 550 ℃ of following roasting 4h
2Graininess Al
2O
3-TiO
2Spherical complex carrier.
Step 4
To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 6mmol/L-7mmol/L
2PdCl
4Acid solution dipping, again with the deionized water of slow drip with catalyst wash to there not being Cl
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 4h, it is 0.15wt%-0.21wt% that the 3-4h that under hydrogen atmosphere, reduces at last obtains palladium content, thickness is the catalyst of 140 μ m-148 μ m.
Another preparation method of the doping type palladium of anthraquinone hydrogenation of the present invention/aluminium oxide titanium catalyst, specifically carry out according to following steps:
Step 1
At Al (NO
3)
3In the solution, adding 10% ammonia spirit, is in the gel that this obtains, to add polyglycol solution again at 10 o'clock to pH, stirs 2h, centrifugalizes after placing 24h, and sediment in 120 ℃ of dry 2h down, then at 550 ℃ of following roasting 4h, is obtained Al
2O
3Carrier.
Step 2
With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
With composite oxide carrier Al
2O
3-TiO
2With Zr (NO
3)
4 Solution impregnation 120 ℃ of oven dry down, obtains containing ZrO behind 550 ℃ of following roasting 4h then
2Graininess Al
2O
3-TiO
2Spherical complex carrier.
Step 4
To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L-8mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 3-4h, it is 0.18wt%-0.22wt% that the 3-4h that under hydrogen atmosphere, reduces at last obtains palladium content, thickness is the catalyst of 148 μ m-155 μ m.
The catalyst characterization method: with the catalyst for preparing 260 ℃ vacuumize handle 3h after, under liquid nitrogen temperature (196 ℃), carry out N
2Determining adsorption is with the specific area of BET equation calculation sample, with BJH method calculated pore and pore size distribution.Utilize electron microprobe examination to do radially from outside to inside microcell scanning of cross section, measure catalyst cross section palladium content radially with spectroscopy, to confirm to contain the thickness of palladium layer to going back the ortho states catalyst.
The palladium catalyst content assaying method is: catalyst sample is crushed to below 100 orders, in 105～110 ℃ of dry 2h, takes by weighing the H that the 0.1g sample adds 7.5mL after the cooling
2SO
4(9mol/L) solution and 2.5mL H
3PO
4(9mol/L) solution, heating is cooled to room temperature until the solution clarification.Solution is moved in the 100ml volumetric flask; Add ethylenediamine tetra-acetic acid (3%) solution 5mL, ascorbic acid (1%) solution 2mL and KI (20%) solution 10mL, dilution is settled to scale, shakes up; Behind the colour developing 15min; To contain the aluminium blank is reference, records absorbance in wavelength 490nm place, is calculated the content of palladium in the catalyst sample by calibration curve.
Being characterized as of the catalyst that obtains according to said method: catalyst B ET specific area is 65～300m
2/ g, pore volume are 0.35～1.0mL/g, and the aperture is at 9～25nm, and the palladium layer thickness is 150 ± 10 μ m, and the content of palladium is 0.2 ± 0.05wt%.
Catalyst performance adopts micro fixed-bed reactor to estimate.The working solution composition that uses is: 2-EAQ (EAQ) content 140g/L, and solvent is with the mixture of trioctyl phosphate (TOP) and heavy aromatics, and ratio is 25/75; The working solution consumption is 240mL; Flow-control is at 7.5L/hr, and reaction pressure is 0.3MPa, and reaction temperature is 50 ℃.
The technical indicator that obtains catalyst according to said method is: catalyst granules is that grey black is spherical, and size is 2.5～3.5mm, and bulk density is at 0.62 ± 0.03kg/L, and average crushing strength is 90N/, and the catalytic activity index is>=5.0kgH
2O
2(100%)/kgCat.d.
Fig. 1 is shown by the result that for the temperature variant curve of hydrogenation efficiency of the catalyst for preparing under the optimum condition this catalyst hydrogenation efficiency is higher, and 58 ℃ reach as high as 9.8gH
2O
2/ L.
Fig. 2 is the total effective anthraquinone content of system with the change curve in reaction time, can be known by figure, and system's effective anthraquinone stable content shows the selection of catalysts property for preparing and stable higher under this catalyst.
Embodiment 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 540 ℃ of roasting 2h, again in 950 ℃ of roasting 4h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier; The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 500 ℃ of roasting 3h, reduction 3h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.20wt%, and thickness is the catalyst sample of 150 μ m, and the hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.80g H
2O
2/ L, activity is 5.26kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Embodiment 2
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 540 ℃ of roasting 2h, again in 950 ℃ of roasting 4h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier; The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 8mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 550 ℃ of roasting 4h, reduction 4h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.23wt%, and thickness is the catalyst sample of 160 μ m, and the hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.80g H
2O
2/ L, activity is 5.24kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Embodiment 3
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 540 ℃ of roasting 2h, again in 950 ℃ of roasting 4h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier; The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7.5mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 520 ℃ of roasting 3.5h, reduction 3.5h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.21wt%, and thickness is the catalyst sample of 156 μ m, and the hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.81g H
2O
2/ L, activity is 5.24kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Embodiment 4
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 15% ammoniacal liquor to pH value at 90 ℃ is 8.0, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 60 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier; With Al
2O
3Carrier is with the dilution heat of sulfuric acid dipping of titanium sulfate, and washing to solution behind the stirring 30min does not have SO
4 2-, dry 12h under 120 ℃ again in 550 ℃ of following roasting 4h, makes composite oxide carrier Al
2O
3-TiO
2With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 550 ℃ of roasting 2h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier; The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 9mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 550 ℃ of roasting 3h, reduction 3h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.25wt%, and thickness is the catalyst sample of 146 μ m.The hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.92g H
2O
2/ L, activity is 5.35kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With the composite oxide carrier Al that obtains
2O
3-TiO
2Use ZrOCl
2The saturated dipping of solution adds urea liquid behind the stirring 8h, and reaction 10h filters, washs and remove Cl under 60 ℃
-, behind 120 ℃ of dry 5h,, obtain containing ZrO again at 550 ℃ of following roasting 4h
2Graininess Al
2O
3-TiO
2Spherical complex carrier; To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 6mmol/L
2PdCl
4Acid solution dipping, again with the deionized water of slow drip with catalyst wash to there not being Cl
-The back oven dry, then at 500 ℃ of roasting 4h, reduction 3h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.15wt%, and thickness is the catalyst sample of 140 μ m.The hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 9.02g H
2O
2/ L, activity is 5.41kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With the composite oxide carrier Al that obtains
2O
3-TiO
2Use ZrOCl
2The saturated dipping of solution adds urea liquid behind the stirring 8h, and reaction 10h filters, washs and remove Cl under 60 ℃
-, behind 120 ℃ of dry 5h,, obtain containing ZrO again at 550 ℃ of following roasting 4h
2Graininess Al
2O
3-TiO
2Spherical complex carrier; To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L
2PdCl
4Acid solution dipping, again with the deionized water of slow drip with catalyst wash to there not being Cl
-The back oven dry, then at 550 ℃ of roasting 4h, reduction 4h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.21wt%, and thickness is the catalyst sample of 148 μ m.The hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.98g H
2O
2/ L, activity is 5.37kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With the composite oxide carrier Al that obtains
2O
3-TiO
2Use ZrOCl
2The saturated dipping of solution adds urea liquid behind the stirring 8h, and reaction 10h filters, washs and remove Cl under 60 ℃
-, behind 120 ℃ of dry 5h,, obtain containing ZrO again at 550 ℃ of following roasting 4h
2Graininess Al
2O
3-TiO
2Spherical complex carrier; To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 6.5mmol/L
2PdCl
4Acid solution dipping, again with the deionized water of slow drip with catalyst wash to there not being Cl
-The back oven dry, then at 520 ℃ of roasting 4h, reduction 3.5h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.18wt%, and thickness is the catalyst sample of 146 μ m.The hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.92g H
2O
2/ L, activity is 5.42kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Embodiment 8
At Al (NO
3)
3In the solution, adding 10% ammonia spirit, is in the gel that this obtains, to add polyglycol solution at 10 o'clock to pH, stirs 2h, centrifugalizes after placing 24h, and sediment in 120 ℃ of dry 2h down, then at 550 ℃ of following roasting 4h, is obtained Al
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With composite oxide carrier Al
2O
3-TiO
2With Zr (NO
3)
4 Solution impregnation 120 ℃ of oven dry down, obtains containing ZrO behind 550 ℃ of following roasting 4h then
2Graininess Al
2O
3-TiO
2Spherical complex carrier; To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 500 ℃ of roasting 3h, reduction 3h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.18wt%, and thickness is the catalyst sample of 148 μ m.The hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.54g H
2O
2/ L, activity is 5.12kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Embodiment 9
At Al (NO
3)
3In the solution, adding 10% ammonia spirit, is in the gel that this obtains, to add polyglycol solution again at 10 o'clock to pH, stirs 2h, centrifugalizes after placing 24h, and sediment in 120 ℃ of dry 2h down, then at 550 ℃ of following roasting 4h, is obtained Al
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With composite oxide carrier Al
2O
3-TiO
2With Zr (NO
3)
4 Solution impregnation 120 ℃ of oven dry down, obtains containing ZrO behind 550 ℃ of following roasting 4h then
2Graininess Al
2O
3-TiO
2Spherical complex carrier; To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 8mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 550 ℃ of roasting 4h, reduction 4h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.22wt%, and thickness is the catalyst sample of 155 μ m.The hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.51g H
2O
2/ L, activity is 5.14kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
At Al (NO
3)
3In the solution, adding 10% ammonia spirit, is in the gel that this obtains, to add polyglycol solution again at 10 o'clock to pH, stirs 2h, centrifugalizes after placing 24h, and sediment in 120 ℃ of dry 2h down, then at 550 ℃ of following roasting 4h, is obtained Al
2O
3Carrier; With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2With composite oxide carrier Al
2O
3-TiO
2With Zr (NO
3)
4 Solution impregnation 120 ℃ of oven dry down, obtains containing ZrO behind 550 ℃ of following roasting 4h then
2Graininess Al
2O
3-TiO
2Spherical complex carrier; To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7.5mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 520 ℃ of roasting 3.5h, reduction 3.5h promptly gets under hydrogen atmosphere at last.
Content through detecting palladium is 0.20wt%, and thickness is the catalyst sample of 151 μ m.The hydrogenation efficiency that records the anthraquinone hydrogenation of this catalyst according to aforementioned catalyst activity evaluation method is 8.56g H
2O
2/ L, activity is 5.22kg H
2O
2(100%)/and kg.cat.d, catabolite＜0.30g/kg H
2O
2(27.5%).
Claims (5)
1. the doping type palladium of an anthraquinone hydrogenation/aluminium oxide titanium catalyst is characterized in that, is made up of the oxide of carrier, main active component, barium and/or chromium; Said carrier is Al
2O
3-TiO
2Composite oxides, Al
2O
3-TiO
2TiO in the composite oxides
2Shared mass fraction is 3%～30%, Al
2O
3-TiO
2Al in the composite oxides
2O
3Shared mass fraction is 60%～95%, and all the other are impurity; Said main active component is Al
2O
3The addition of the oxide of said barium and/or chromium is 0.5%～15% of a carrier quality; Specific surface area of catalyst is 65m
2/ g～300m
2/ g, pore volume are 0.35mL/g～1.0mL/g, and the aperture is at 9nm～25nm, and the palladium layer thickness is 150 ± 10 μ m, and palladium content is 0.2 ± 0.05wt%.
2. the preparation method of the doping type palladium of the said anthraquinone hydrogenation of claim 1/aluminium oxide titanium catalyst is characterized in that, specifically carries out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier;
Step 2
The Al that step 1 is obtained
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
The composite oxide carrier Al that step 2 is obtained
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 540 ℃ of roasting 2h, again in 950 ℃ of roasting 4h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier;
Step 4
The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L-8mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 3-4h, reduction 3-4h promptly gets under hydrogen atmosphere at last.
3. the preparation method of the doping type palladium of the said anthraquinone hydrogenation of claim 1/aluminium oxide titanium catalyst is characterized in that, specifically carries out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 15% ammoniacal liquor to pH value at 90 ℃ is 8.0, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 60 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier;
Step 2
With Al
2O
3Carrier is with the dilution heat of sulfuric acid dipping of titanium sulfate, and washing to solution behind the stirring 30min does not have SO
4 2-, dry 12h under 120 ℃ again in 550 ℃ of following roasting 4h, makes composite oxide carrier Al
2O
3-TiO
2
Step 3
With the composite oxide carrier Al that obtains
2O
3-TiO
2With Ba (NO
3)
2Solution impregnation is dried to constant weight at 60 ℃ then, in 550 ℃ of roasting 2h, obtains containing the graininess Al of BaO
2O
3-TiO
2Spherical complex carrier;
Step 4
The graininess Al that will contain BaO
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 9mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 550 ℃ of roasting 3h, reduction 3h promptly gets under hydrogen atmosphere at last.
4. the preparation method of the doping type palladium of the said anthraquinone hydrogenation of claim 1/aluminium oxide titanium catalyst is characterized in that, specifically carries out according to following steps:
Step 1
Adopt Al
2(SO
4)
3The aqueous solution is raw material, and down dripping 20% ammoniacal liquor to pH value at 90 ℃ is 7.5, stirs 3h, filters, and spending does not have chlorion in deionised water to the solution, and dropping concentration is 0.3% HNO in filter cake subsequently
3To the pH value be 3.0, process boehmite colloidal sol after fully stirring, this colloidal sol in 50 ℃ of dry 24h, at 550 ℃ of roasting 2h, is obtained Al then
2O
3Carrier;
Step 2
With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
With the composite oxide carrier Al that obtains
2O
3-TiO
2Use ZrOCl
2The saturated dipping of solution adds urea liquid behind the stirring 8h, and reaction 10h filters, washs and remove Cl under 60 ℃
-, behind 120 ℃ of dry 5h,, obtain containing ZrO again at 550 ℃ of following roasting 4h
2Graininess Al
2O
3-TiO
2Spherical complex carrier;
Step 4
To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 6mmol/L-7mmol/L
2PdCl
4Acid solution dipping, again with the deionized water of slow drip with catalyst wash to there not being Cl
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 4h, reduction 3-4h promptly gets under hydrogen atmosphere at last.
5. the preparation method of the doping type palladium of the said anthraquinone hydrogenation of claim 1/aluminium oxide titanium catalyst is characterized in that, specifically carries out according to following steps:
Step 1
At Al (NO
3)
3In the solution, adding 10% ammonia spirit, is in the gel that this obtains, to add polyglycol solution again at 10 o'clock to pH, stirs 2h, centrifugalizes after placing 24h, and sediment in 120 ℃ of dry 2h down, then at 550 ℃ of following roasting 4h, is obtained Al
2O
3Carrier;
Step 2
With Al
2O
3Carrier takes out after flooding 5h with butyl titanate, again in 550 ℃ of following roasting 4h, obtains composite oxide carrier Al behind 120 ℃ of dry 20h
2O
3-TiO
2
Step 3
With composite oxide carrier Al
2O
3-TiO
2With Zr (NO
3)
4Solution impregnation 120 ℃ of oven dry down, obtains containing ZrO behind 550 ℃ of following roasting 4h then
2Graininess Al
2O
3-TiO
2Spherical complex carrier;
Step 4
To contain ZrO
2Graininess Al
2O
3-TiO
2Spherical complex carrier cooling back adds the Na of 7mmol/L-8mmol/L
2PdCl
4The acid solution dipping, the deionized water with slow drip is washed till no Cl again
-The back oven dry, then at 500 ℃ of-550 ℃ of roasting 3-4h, reduction 3-4h promptly gets under hydrogen atmosphere at last.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210120069.9A CN102658134B (en) | 2012-04-23 | 2012-04-23 | Doping-type Pd/aluminum oxide titanium catalyst hydrogenated through anthraquinone process and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210120069.9A CN102658134B (en) | 2012-04-23 | 2012-04-23 | Doping-type Pd/aluminum oxide titanium catalyst hydrogenated through anthraquinone process and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102658134A true CN102658134A (en) | 2012-09-12 |
| CN102658134B CN102658134B (en) | 2014-05-21 |
Family
ID=46767791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210120069.9A Expired - Fee Related CN102658134B (en) | 2012-04-23 | 2012-04-23 | Doping-type Pd/aluminum oxide titanium catalyst hydrogenated through anthraquinone process and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102658134B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110523407A (en) * | 2019-08-26 | 2019-12-03 | 岳阳聚成化工有限公司 | Regeneration method for regenerated catalyst of cycle working fluid and preparation method thereof and cycle working fluid |
| CN112717926A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone hydrogenation and preparation method and application thereof |
| CN113750989A (en) * | 2021-10-11 | 2021-12-07 | 浙江大学 | Catalyst suitable for catalyzing biomass oil phenolic compound to prepare oxygenated product through hydrogenation, and preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497040A (en) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof |
-
2012
- 2012-04-23 CN CN201210120069.9A patent/CN102658134B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497040A (en) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ASSANA GAMPINE ET AL.: "Catalytic Hydrodechlorination of Chlorocarbons. 2. Ternary OxideSupports for Catalytic Conversions of 1,2-Dichlorobenzene", 《JOURNAL OF CATALYSIS》, vol. 179, 31 December 1998 (1998-12-31), pages 315 - 325 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110523407A (en) * | 2019-08-26 | 2019-12-03 | 岳阳聚成化工有限公司 | Regeneration method for regenerated catalyst of cycle working fluid and preparation method thereof and cycle working fluid |
| CN110523407B (en) * | 2019-08-26 | 2022-08-02 | 岳阳聚成化工有限公司 | Catalyst for recycling working fluid, preparation method thereof and recycling working fluid recycling method |
| CN112717926A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone hydrogenation and preparation method and application thereof |
| CN113750989A (en) * | 2021-10-11 | 2021-12-07 | 浙江大学 | Catalyst suitable for catalyzing biomass oil phenolic compound to prepare oxygenated product through hydrogenation, and preparation and application thereof |
| CN113750989B (en) * | 2021-10-11 | 2023-11-17 | 浙江大学 | Catalyst suitable for catalyzing biomass oil phenolic compounds to prepare oxygenated products by hydrogenation, and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102658134B (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105688974B (en) | One kind is with SBA-15/TiO2For the denitrating catalyst and preparation method thereof of carrier | |
| CN104801333B (en) | A kind of preparation method of loading type nickel-based catalyst | |
| CN101850273B (en) | Structured catalyst for synthesizing oxalate by CO gaseous-phase coupling and preparation method thereof | |
| CN102728374B (en) | Preparation method of hydrotreatment catalyst | |
| CN101543778A (en) | Noble metal catalyst based on spherical silicon-containing alumina, and preparation method thereof | |
| CN1175931C (en) | Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof | |
| CN102728373B (en) | Preparation method of hydrotreating catalyst | |
| CN104689830B (en) | A kind of catalyst for alkynes and diolefin hydrogenate in mixed olefins | |
| CN105562000B (en) | A kind of arsenic removal catalyst and the preparation method and application thereof | |
| CN102343270A (en) | Hydrogenation catalyst with active metal components in layered distribution and preparation method thereof | |
| CN107303488B (en) | Ester hydrogenation catalyst, preparation method and application thereof | |
| CN102302934A (en) | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst | |
| CN102658134B (en) | Doping-type Pd/aluminum oxide titanium catalyst hydrogenated through anthraquinone process and preparation method thereof | |
| CN102989452B (en) | Carbon dioxide pre-hydrogenation catalyst containing composite carrier and preparation method thereof | |
| CN110075907A (en) | A kind of ammoxidation catalyst and preparation method thereof for diesel car tail gas refining | |
| CN107303484A (en) | The preparation method and hydrotreating catalyst of a kind of siliceous macropore alumina supporter | |
| CN100387335C (en) | Palladium-aluminium oxide catalyst and its preparation process | |
| CN109261153B (en) | Supported nickel-based catalyst and preparation method and application thereof | |
| CN106345488A (en) | Copper-manganese-cerium composite oxide FCC regenerated flue gas combustion-supporting denitration auxiliary agent and preparation method thereof | |
| CN111530473B (en) | Catalyst for preparing ethanol by ethyl acetate hydrogenation and preparation method and application thereof | |
| CN108067228B (en) | Propane dehydrogenation catalyst and preparation method thereof | |
| CN109529912A (en) | Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof | |
| CN101745383B (en) | Deep hydrogenation dearomatization catalyst and preparation method thereof | |
| CN112206816A (en) | Composite molecular sieve catalyst for preparing olefin by propane dehydrogenation and preparation method thereof | |
| CN102794178B (en) | A kind of selective hydrogenation catalyst and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yu Jianqiang Inventor after: Cao Fenghua Inventor after: Zu Lei Inventor after: Yan Chunqin Inventor before: Yu Jianqiang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: YU JIANQIANG TO: YU JIANQIANG CAO FENGHUA ZU LEI YAN CHUNQIN |
|
| 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 |
Granted publication date: 20140521 Termination date: 20150423 |
|
| EXPY | Termination of patent right or utility model |