CN104667916A - Method for preparing catalytic wet oxidation catalyst - Google Patents
Method for preparing catalytic wet oxidation catalyst Download PDFInfo
- Publication number
- CN104667916A CN104667916A CN201310620794.7A CN201310620794A CN104667916A CN 104667916 A CN104667916 A CN 104667916A CN 201310620794 A CN201310620794 A CN 201310620794A CN 104667916 A CN104667916 A CN 104667916A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- accordance
- carrier
- amino acid
- roasting
- 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
Abstract
The invention discloses a method for preparing a catalytic wet oxidation catalyst. The catalyst comprises a carrier, an active metal ingredient and an auxiliary, wherein the active metal ingredient is one or more of Pt, Pd, Rh and Ru, and the auxiliary is rare-earth metal; and the carrier uses activated carbon as a core, and amorphous alumina as a shell. The preparation method comprises the following steps: introducing amino acid treated activated carbon slurry into the process of gelling amorphous alumina, aging after gelling, and carrying out hydrothermal treatment; filtering, washing and drying to obtain a carrier material; and preparing the carrier, and loading the active metal ingredient and the auxiliary. When being used for a catalytic wet oxidation reaction, the catalyst has relatively high reaction activity and using stability, and the service life of the catalyst can be prolonged.
Description
Technical field
The present invention relates to a kind of preparation method of catalytic wet oxidation catalyst, particularly contain the preparation method of the catalytic wet oxidation catalyst of active carbon and amorphous alumina.
Background technology
Along with the increasingly stringent of global environmental regulation, the Con trolling index of sewage qualified discharge requires more and more higher, under this form, waste water treatment by catalytic oxidation more and more obtains attention and the employing of people, as the CWO, catalytic and oxidative electrolysis technology, photochemical catalytic oxidation, advanced oxidation etc. of high-concentration sewage.In waste water catalytic oxidation process, for obtain desirable treatment effect and by reduce reaction temperature, reaction pressure to keep lower wastewater treatment expense, preparation have high-activity component, high strength, high stability cheap catalyst become undoubtedly waste water catalytic oxidation technologies apply key.
The catalyst of waste water catalytic oxidation is mainly divided into homogeneous catalyst and heterogeneous solid catalyst two class.
Homogeneous catalyst mainly comprises the Fenton reagent, the Fe that produce oxygen radical
3+, Cu
2+, the metal ion such as cobalt and manganese, by means of the effect of these homogeneous catalysts, organic component in waste water, sulfide, ammonia nitrogen etc. are oxidized into low molecular acid (low mass molecule alcohol or carbon dioxide), sulfate or thiosulfate, nitrogen etc. by oxide isolations such as air, oxygen, ozone, hydrogen peroxide, make waste water reach the processing intent of decarburization, desulfurization and denitrogenation.Homogeneous oxidation catalyst preparation and use procedure comparatively simple, the slaines such as iron, copper, cobalt, manganese generally directly can be selected to be made into the aqueous solution or directly to put in handled waste water, and discharge or the use of regeneration Posterior circle by the water outlet after processing.Adopt homogeneous catalytic oxidation, because metal active constituent can fully dissolve and disperse in waste water, generally can reach comparatively stable water treatment effect, but also exist that reagent consumption is large, operating cost is high, the serious problems such as metal loss and secondary pollution, cause its application to be subject to larger restriction.
Heterogeneous solid catalyst mainly with active carbon, molecular sieve, amorphous alumina, titanium dioxide etc. for carrier, make with one or more in alkali metal, alkaline-earth metal, transition metal or Pt, Pd noble metal the catalyst that active component formed.Active carbon be made up of carbonaceous material black, hole is flourishing, specific area large, a class microcrystalline carbon of high adsorption capacity.Activated carbon property is stablized, and acidproof, alkaline-resisting, heat-resisting, water insoluble or organic solvent, easily regenerates, and is a kind of environmentally friendly adsorbent, is widely used in the fields such as Industrial " three Waste " improvement, food, medicine, carrier, semiconductor, battery and power storage.Mostly select active carbon as carrier for the heterogeneous solid catalyst of wastewater treatment at present, but the catalyst anti-wear performance selecting activated carbon supported metal to prepare is poor, mechanical strength is not high, and the metal of load easily runs off, and the effect of activated-carbon catalyst is made a discount.Amorphous alumina is because having good chemical stability, pore volume is large, there is the advantages such as certain acidity, pore size distribution$ is concentrated, mechanical strength is large, corrosion-resistant, be widely used at catalytic field, but there is the little shortcoming of specific surface in amorphous alumina, to organic absorption and conversion capability relatively little.
CN201110225789.7 discloses a kind of method utilizing discarded active amorphous alumina preparation benzene adsorption material, it be by useless active amorphous aluminium oxide through cleaning, filter, after drying, adopt cryogenic seal heat treatment mode to prepare a kind of active amorphous aluminium oxide/absorbent charcoal composite material, to benzene, there is good adsorption effect.The method is by the organic matter carbonizing of amorphous alumina inside, and active carbon is mainly distributed in the duct of amorphous alumina, so not only can block the duct of aluminium oxide, and such generated active carbon skewness in aluminium oxide.
CN201110255525.6 discloses the preparation method of a kind of active amorphous aluminium oxide/absorbent charcoal composite material, be by waste aluminum sludge, active carbon, binding agent through mixing, granulation, old, shaping, dry, sinter, rinsing, drying and other steps make active amorphous aluminium oxide/absorbent charcoal composite material.The method belongs to salic species and active carbon physical mixing processes, and aluminium oxide and active carbon disperse uneven; And the mud impurity content used is high, the amorphous alumina character of gained is unstable, cannot repeat, complex structure.
CN201010267074.3 discloses a kind of preparation method of activated alumina composite reactive Carbon Materials, with aluminium hydroxide, active carbon and binding agent for raw material, through mixing, granulation, old, shaping, dry, sinter, rinsing, drying and other steps, the composite obtained like this is still the physical mixture of aluminium oxide and active carbon, aluminium oxide and active carbon disperse uneven, and its combination property also needs further raising.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method with the catalytic wet oxidation catalyst that catalytic performance is good, anti-wear performance is strong, stability in use is good.
The preparation method of catalytic wet oxidation catalyst of the present invention, this catalyst comprises carrier, active metal component and auxiliary agent, wherein with one or several in Pt, Pd, Rh, Ru for active component, rare earth metal is auxiliary agent, and preparation process comprises:
(1) 150 order ~ 300 order active carbons are adopted amino acid process, then pull an oar;
(2) in amorphous alumina plastic process, introduce the active carbon slurries that step (1) obtains;
(3) material after the plastic that obtains of step (2) carries out aging, after hydrothermal treatment consists, refilters, washs, dry, obtains carrier material;
(4) carrier material of step (3) gained is made catalyst carrier, preferably at least adopts one of following method:
A, by the carrier material of step (3) gained, roasting under inert gas shielding, obtains catalyst carrier;
B, by shaping for the carrier material of step (3) gained, after drying, roasting under inert gas shielding, obtains catalyst carrier;
C, by carrier material roasting under inert gas shielding of step (3) gained, and then through shaping, after drying, roasting under inert gas shielding, obtains catalyst carrier;
(5) impregnated activated metal component and auxiliary agent in the catalyst carrier of step (4) gained, then dry, roasting under inert gas shielding, obtains catalytic wet oxidation catalyst.
Catalytic wet oxidation catalyst of the present invention, comprise carrier, active metal component and auxiliary agent, wherein with one or several in Pt, Pd, Rh, Ru for active component, rare earth metal is auxiliary agent, carrier be with 150 order ~ 300 object active carbons be core, with amorphous alumina for shell, wherein active carbon accounts for 10% ~ 70% of vehicle weight, be preferably 30% ~ 70%, aluminium oxide accounts for 30% ~ 90% of vehicle weight, is preferably 30% ~ 70%.
In catalyst of the present invention, with one or several in precious metals pt, Pd, Rh, Ru for active component, rare earth metal is auxiliary agent, with the weight of catalyst for benchmark, the content of noble metal counts 0.01% ~ 1.0% with element, and the content of rare earth metal counts 1.0% ~ 15.0% with element.
In catalyst of the present invention, described rare earth metal is one or more in lanthanum, cerium, praseodymium, neodymium.
Catalyst of the present invention can be do not need shaping powder catalyst, also can be preformed catalyst.The granularity of powder catalyst is generally 0.05 ~ 0.2mm.Preformed catalyst can determine the size of granularity as required, is generally 0.5 ~ 8.0mm.
The character of preformed catalyst of the present invention is as follows: specific area is 200 ~ 1000m
2/ g, pore volume is 0.3 ~ 1.8cm
3/ g, rate of wear <3wt%, side pressure strength is 100 ~ 250N/cm.
Step of the present invention (1) described active carbon can select conventional Powdered Activated Carbon commodity, as all kinds of wood activated charcoal, active fruit shell carbon, active carbon from coal; Also can select with wooden material, mineral material, plastics and discarded object, as the various activated carbon products that timber, wood chip, charcoal, coconut husk, fruit stone, shell, coal, gangue, petroleum coke, asphalt, polyvinyl chloride, polypropylene, organic resin, damaged tire, excess sludge etc. obtain through traditional preparation methods.The active carbon used in the present invention is powdered active carbon, granularity 150 ~ 300 order, specific area 500 ~ 3000m
2/ g, pore volume 0.5 ~ 1.8cm
3/ g, average pore radius 1 ~ 10nm.
In the inventive method, the making beating of active carbon described in step (1) adopts conventional method to carry out, general adopt add water, one or more in low-carbon alcohols pull an oar, wherein low-carbon alcohols to be carbon number be in the monohydric alcohol of 1 ~ 5 one or more.
In the inventive method, step (1) active carbon first adopts amino acid process, then pulls an oar.Described amino acid is hydrophilic amino acid, such as, in glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid one or more, preferred C number is less than the hydrophilic amino acid of the long-chain of 10.Such as aspartic acid, glutamic acid, lysine etc.Described amino acid consumption accounts for 2% ~ 50% of activated carbon weight, is preferably 5% ~ 20%.Amino acid can directly mix with active carbon by amino acid process active carbon, also amino acid can be dissolved in solvent and add active carbon again, solvent is wherein water, one or more in low-carbon alcohols (namely carbon number is the monohydric alcohol of 1 ~ 5).During amino acid process active carbon, its liquid-solid volume ratio below 10, preferably 1 ~ 5.After amino acid process active carbon, excessive liquid phase is preferably crossed and is filtered, and then pulls an oar.Making beating can adopt conventional method to carry out, general adopt add water, one or more in low-carbon alcohols pull an oar, wherein low-carbon alcohols to be carbon number be in the monohydric alcohol of 1 ~ 5 one or more.
The plastic process of the amorphous alumina described in step of the present invention (2) can be undertaken by process well known to those skilled in the art.The plastic process of amorphous alumina is generally the neutralization reaction process of acid material and alkaline material.Plastic process can adopt the mode of the continuous acid-base titration of soda acid, also can adopt two kinds of materials and the mode of stream neutralization.
In step of the present invention (2), aluminium oxide plastic is the process adopting aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent to carry out neutralization reaction, aluminum soluble salt wherein used is one or more in aluminium chloride, aluminum sulfate, aluminum nitrate, acidic precipitation agent used is generally one or several in hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, carbon dioxide etc., and alkaline precipitating agent used is generally one or several in sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor etc.During aluminium oxide plastic also can adopt meta-aluminate (such as sodium metaaluminate and/or potassium metaaluminate) and acid aluminium salt (in such as aluminium chloride, aluminum nitrate, aluminum sulfate one or more) to carry out and the method for plastic.Described plastic process is generally carried out at room temperature ~ 85 DEG C, is comparatively suitably for 40 ~ 80 DEG C, is preferably 50 ~ 70 DEG C.Described plastic process is generally carried out under certain pH value condition, and typical pH is 6.0 ~ 10.0, is comparatively suitably for 7.0 ~ 9.5, is preferably 7.5 ~ 9.0.Aging described in step (3), condition is as follows: pH is 6.0 ~ 10.0, and be preferably 7.0 ~ 9.5, ageing time 0.25 ~ 8 hour, is comparatively adapted at 0.5 ~ 5 hour, and be preferably 1 ~ 3 hour, aging temperature is room temperature ~ 85 DEG C, is preferably 40 ~ 80 DEG C.Temperature time aging and pH with in time temperature preferably identical with pH.
In step of the present invention (2), the incorporation way of the mixture of step (1) gained adopts the one or more combination of following manner: this mixture, in plastic neutralization reaction process, adds in plastic cans by (1) continuously; (2) this mixture is first joined in plastic cans, then will prepare in the acid material of amorphous alumina and alkaline material and plastic; (3) one or more with plastic material of this mixture are mixed, then in plastic material and plastic.
In step of the present invention (3), before hydrothermal treatment consists, preferably after filtration or heating concentration, remove excessive moisture and soluble species.Wherein said heating simmer down to is heating steps (2) products obtained therefrom at 90 ~ 110 DEG C, and good temperature is 95 ~ 105 DEG C, preferably 98 ~ 100 DEG C, is heated to immobilising paste shape.
In step of the present invention (3), described hydrothermal treatment consists is carried out in closed container, and the temperature of hydrothermal treatment consists is 90 ~ 300 DEG C, preferably 100 ~ 250 DEG C, be preferably 150 ~ 210 DEG C, described hydrothermal treatment consists is carried out under the pressure condition of self that produces when material treatment temperature.Described hydrothermal conditions is 0.5 ~ 48h, is 1 ~ 36h, preferably 2 ~ 24h preferably.
In step of the present invention (3), the mode of washing of described material is known in those skilled in the art, can select making beating washing, add the mode such as water washing, lower alcohols washing when filtering, the temperature of washing should in the temperature range of room temperature ~ 90 DEG C, preferably 50 ~ 70 DEG C.The washing of described material is generally carried out in the scope that pH is 1.0 ~ 9.0, and preferred pH is 4.0 ~ 8.5.Material described in step of the present invention (3) should not contain or contain the heteroion of seldom amount after washing, filtration, and heteroion comprises Na
+, Cl
-, SO
4 2-, NO
3 -, K
+deng in one or more.
In step of the present invention (3), described material is after washing, filtering, filter cake carries out drying, and drying mode can adopt natural drying, oven drying, spraying dry, microwave drying or infra-red drying, and the general drying condition adopted is as follows: drying 1 ~ 15 hour at 50 ~ 150 DEG C.
In step of the present invention (4), method A obtains powdered catalytic agent carrier without shaping roasting direct.Roasting condition described in method A is as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
In step of the present invention (4), shaping described in method B and method C can be carried out as required, and be generally strip, cylindric, spherical, irregular strip, special-shaped ball etc., granularity can be determined as required, is generally 0.5 ~ 8.0mm.In described forming process, shaping assistant can be added as required as one or more in adhesive, peptization acid, extrusion aid etc.
In step of the present invention (4), the drying condition described in method B is generally at 80 ~ 200 DEG C, and dry 1 ~ 15 hour, sintering temperature was generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
In step of the present invention (4), in method C, by carrier material roasting under inert gas shielding of step (3) gained, described roasting condition is as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.And then through shaping, after drying, roasting under inert gas shielding; obtain catalyst carrier, the drying condition after shaping is as follows: at 80 ~ 200 DEG C, dry 1 ~ 15 hour; roasting condition is as follows: sintering temperature is generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
In the present invention, under inert gas shielding, carry out roasting, selected inert gas is generally nitrogen or argon gas.
In step of the present invention (5), carrier impregnation metal component and auxiliary agent can be spray, and also can be saturated dippings, also can be supersaturation dippings.
In step of the present invention (5), after catalyst soakage, drying condition is generally at 80 ~ 200 DEG C, and dry 1 ~ 15 hour, sintering temperature was generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
In step of the present invention (5), when carrier impregnation active metal component and auxiliary agent, the maceration extract containing active metal and auxiliary agent is usually adopted to flood.Maceration extract adopts conventional method preparation, is dissolved in solvent formulated by noble metal (in platinum, palladium, ruthenium and rhodium one or more) and the predecessor of rare earth metal.
In the preparation process of catalyst carrier of the present invention, pull an oar again after being employing amino acid process active carbon, then introduce in the plastic process of amorphous alumina, such amino acid is adsorbed on the surfaces externally and internally of active carbon uniformly, the amino acid be mixed in the middle of aluminium oxide and active carbon is made to decompose charing by follow-up roasting process, the active carbon of new formation connects aluminium oxide and active carbon, make the combination of active carbon and aluminium oxide tightr, the inner surface of the new Activated Carbon Modification former active carbon of the amino acid on active carbon inner surface through being decomposed to form, add the adsorption activity position of active carbon inner surface.Therefore, amino acid process active carbon, can accelerating oxidation aluminium closely coating active charcoal, is conducive to the mechanical strength and the abrasion resisting performance that improve catalyst, and improves the utilization rate of the inner surface of active carbon, is conducive to the activity and the stability that improve catalyst.In use, the not tolerant of reaction species first enters stratum nucleare again by shell, insoluble suspension in reactant first adsorbs and is deposited in shell, hydrothermal treatment consists contributes to the mesopore of aluminium oxide formation rule, contribute to the appearance dirt ability improving shell aluminium oxide, make catalyst have higher reactivity and stability in use, improve the service life of catalyst.
Catalyst preparation process of the present invention is simple, convenient, is easy to operation, is applicable to industrial production.
Detailed description of the invention
The specific area of product of the present invention and pore volume adopt low temperature liquid nitrogen physisorphtion to measure.Rate of wear adopts drum-type abrasion instrument to measure (specifically to see " catalyst support preparation and application technology " (petroleum industry publishing house, in May, 2002, Zhu Hongfa writes, and 4.5.4 saves).Powder carrier and catalyst grain size adopt laser particle size analyzer to measure; Shaping carrier and catalyst grain size adopt sieve method to record.In the present invention, wt% is mass fraction.
Further illustrate preparation method of the present invention below in conjunction with specific embodiment, but scope of the present invention is not only limited to the scope of these embodiments.
Commercially available powdery coconut husk charcoal specific area 928m used in the present invention
2/ g, pore volume 1.0cm
3/ g, average pore radius 1.1nm, iodine sorption value 700mg/g, granularity 200 order.
Embodiment 1
Solid aluminum chloride is joined in distilled water, heat simultaneously and be stirred to dissolving, obtain solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Powdery coconut husk charcoal adds in glutamic acid aqueous solution and mixes, and liquid-solid volume ratio is 3:1, and then add water making beating, obtains slurries (c).(a) is added and after being heated with stirring to 60 DEG C in plastic cans, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, now in tank, add (c), continue to drip (b), control, in 30 minutes, system in tank is added drop-wise to pH=8.0.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour; by material filtering in tank to contents on dry basis 15wt%; material is transferred in autoclave, process 4h under 180 DEG C of conditions, filter; washing is extremely without chlorion; filter, by filter cake at 110 DEG C dry 10 hours, obtain carrier material A-1; then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverizes and sieves and obtains powder carrier J-1.The amount of plastic agents useful for same lists in table 1.
Get carrier material J-1 100 grams; paste is formed with the peptization liquid comes into contact containing nitric acid; extruded moulding; then at 110 DEG C dry 10 hours, roasting after 5 hours under 550 DEG C of conditions under nitrogen protection, with the impregnation fluid containing Pt-Ce; then at 110 DEG C dry 10 hours; under nitrogen protection, roasting 5 hours under 550 DEG C of conditions, obtains catalyst A, and its composition is in table 2.
Embodiment 2
Solid aluminum sulfate is joined in distilled water, heat simultaneously and be stirred to dissolving, obtain solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Powdery coconut husk charcoal adds in glutamic acid aqueous solution and mixes, and liquid-solid volume ratio is 3:1, and then add water making beating, obtains active carbon slurries (c).Get a plastic cans, (a) is added and after being heated with stirring to 60 DEG C in tank, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, open the valve of (c) container, continue to drip (b), control, in 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c), ensure now to be added dropwise to complete.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour; by material in tank at 100 DEG C at baking oven inner drying to contents on dry basis 15wt%; material is transferred in autoclave, process 4h under 180 DEG C of conditions, filter; washing is to sulfate radical-free ion; filter, by filter cake at 110 DEG C dry 10 hours, obtain carrier material A-2; then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverizes and sieves and obtains powder carrier J-2.The amount of plastic agents useful for same lists in table 1.
Get carrier material A-2 100 grams; paste is formed with the peptization liquid comes into contact containing nitric acid; extruded moulding; then at 110 DEG C dry 10 hours, roasting after 5 hours under 550 DEG C of conditions under nitrogen protection, with the impregnation fluid containing Ru-Ce; then at 110 DEG C dry 10 hours; under nitrogen protection, roasting 5 hours under 550 DEG C of conditions, obtains catalyst B, and its composition is in table 2.
Embodiment 3
Solid aluminum sulfate is joined in distilled water, heat simultaneously and be stirred to dissolving, obtain solution (a).Solid sodium metaaluminate being mixed with concentration is 250g Al
2o
3/ L sodium aluminate solution (b).Added in glutamic acid aqueous solution by powdery coconut husk charcoal and mix, liquid-solid volume ratio is 3:1, and then add water making beating, obtains slurries (c).Get a plastic cans, insert after 2L deionized water and stirring is heated to 60 DEG C and add slurries (c), open the valve of container having (a), (b), the pH=8.0 of the hierarchy of control simultaneously, control in 45 minutes, (a) to be dripped off, valve-off.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour; by material filtering in tank to contents on dry basis 15wt%; material is transferred in autoclave, process 4h under 180 DEG C of conditions, filter; washing is to sulfate radical-free ion; filter, by filter cake at 110 DEG C dry 10 hours, obtain carrier material A-3; then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverizes and sieves and obtains powder carrier J-3.The amount of plastic agents useful for same lists in table 1.
Get carrier material A-3 100 grams; paste is formed with the peptization liquid comes into contact containing nitric acid; extruded moulding; then at 110 DEG C dry 10 hours, roasting after 5 hours under 550 DEG C of conditions under nitrogen protection, with the impregnation fluid containing Ru-Ce; then at 110 DEG C dry 10 hours; under nitrogen protection, roasting 5 hours under 550 DEG C of conditions, obtains catalyst C, and its composition is in table 2.
Embodiment 4
Solid aluminum chloride is joined in distilled water, heat simultaneously and be stirred to dissolving, obtain solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Powdery coconut husk charcoal adds in lysine solution and mixes, and liquid-solid volume ratio is 3:1, and then add water making beating, obtains active carbon slurries (c).(a) is added and after being heated with stirring to 60 DEG C in plastic cans, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, now in tank, add (c), continue to drip (b), control, in 30 minutes, system in tank is added drop-wise to pH=8.0.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour; by material in tank at 100 DEG C at baking oven inner drying to contents on dry basis 15wt%; material is transferred in autoclave, process 4h under 180 DEG C of conditions, filter; washing is extremely without chlorion; filter, by filter cake at 110 DEG C dry 10 hours, obtain carrier material A-4; then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverizes and sieves and obtains powder carrier J-4.The amount of plastic agents useful for same lists in table 1.
Get carrier material A-4 100 grams; paste is formed with the peptization liquid comes into contact containing nitric acid; extruded moulding; then at 110 DEG C dry 10 hours, roasting after 5 hours under 550 DEG C of conditions under nitrogen protection, with the impregnation fluid containing Ru-Ce; then at 110 DEG C dry 10 hours; under nitrogen protection, roasting 5 hours under 550 DEG C of conditions, obtains catalyst D, and its composition is in table 2.
Embodiment 5
Solid aluminum sulfate is joined in distilled water, heat simultaneously and be stirred to dissolving, obtain solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Powdery coconut husk charcoal adds in lysine solution and mixes, and liquid-solid volume ratio is 3:1, and then add water making beating, obtains active carbon slurries (c).Get a plastic cans, (a) is added and after being heated with stirring to 60 DEG C in tank, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, open the valve of (c) container, continue to drip (b), control, in 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c), ensure now to be added dropwise to complete.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour; by material in tank at 100 DEG C at baking oven inner drying to contents on dry basis 15wt%; material is transferred in autoclave, process 4h under 180 DEG C of conditions, filter; washing is to sulfate radical-free ion; filter, by filter cake at 110 DEG C dry 10 hours, obtain carrier material A-5; then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverizes and sieves and obtains powder carrier J-5.The amount of plastic agents useful for same lists in table 1.
Get carrier material A-5 100 grams; paste is formed with the peptization liquid comes into contact containing nitric acid; extruded moulding; then at 110 DEG C dry 10 hours, roasting after 5 hours under 550 DEG C of conditions under nitrogen protection, with the impregnation fluid containing Pt-La; then at 110 DEG C dry 10 hours; under nitrogen protection, roasting 5 hours under 550 DEG C of conditions, obtains catalyst E, and its composition is in table 2.
Comparative example 1
Repeat the synthesis of embodiment 2, in plastic process, do not add active carbon and amino acid, obtained comparative catalyst's carrier material PA-1 and powder carrier DF-1, its appearance white.
Preformed catalyst preparation, with embodiment 2, obtains catalyst DA, and its composition is in table 2.
Comparative example 2
By active carbon 100 grams used in embodiment 2, form paste, extruded moulding with the peptization liquid comes into contact containing nitric acid, then at 110 DEG C dry 10 hours, under nitrogen protection, under 550 DEG C of conditions, roasting, after 5 hours, obtained carrier, and its outward appearance is black.Then adopt the impregnated activated metal component of method of embodiment 2, obtain catalyst DB, its composition is in table 2.
Comparative example 3
By active carbon used in embodiment 2 with carrier material PA-1 physical mixed; paste is formed with the peptization liquid comes into contact containing nitric acid; extruded moulding; then at 110 DEG C dry 10 hours; under nitrogen protection, under 550 DEG C of conditions, roasting, after 5 hours, obtains carrier, and wherein activated carbon content is 50wt%; alumina content is 50wt%, and its outward appearance is black.Then adopt the impregnated activated metal component of method of embodiment 2, obtain catalyst DC, its composition is in table 2.
Comparative example 4
Repeat the synthesis of embodiment 2, in plastic process, do not carry out hydrothermal treatment consists, obtained comparative catalyst's carrier material PA-2 and powder carrier DF-2.
The preparation of preformed catalyst carrier and catalyst, with embodiment 2, obtains catalyst carrier DD, and its composition is in table 2.
Comparative example 5
Repeat the synthesis of embodiment 2, in plastic process, do not add amino acid, and do not carry out hydrothermal treatment consists in plastic process, obtained catalyst carrier material PA-3 and powder carrier DF-3.
Preformed catalyst preparation, with embodiment 2, obtains catalyst carrier DZ-E and catalyst DE, and its composition is in table 2.
Table 1 plastic reagent quality
The composition of table 2 catalyst and character
As can be seen from catalyst property in table 2, the monolith character obtained after adopting amino acid process active carbon and hydrothermal treatment consists carrier material is improved.
Be canescence by the carrier material of embodiment of the present invention gained and the outward appearance of carrier, without obvious black, illustrate that active carbon becomes the core of carrier material and carrier.
In the present invention, X-ray photoelectron spectroscopy (XPS) element to embodiment and comparative example 1 gained surfaces of carrier materials is adopted to analyze.From analysis result, the element composition on embodiment gained carrier material A-1 ~ A-5 surface forms substantially identical with PA-1, all has the elemental carbon of trace.This further illustrates, and carrier material of the present invention is core with active carbon, take alumina dry glue as shell.
Simulated wastewater is used to carry out evaluating catalyst.
Preparation sodium sulfite waste water, COD is 12000mg/L pH value of solution is 6 ~ 7, evaluates in small-sized flow reactor.Treatment temperature 45 DEG C, volume space velocity 2.0h
-1, the reaction condition of gas-liquid volume ratio 200 carries out the process of continuous catalysis wet air oxidation to this waste water.Result lists in table 3.
Table 3 evaluation result
| Catalyst is numbered | B | DA | DB | DC | DD | DE |
| COD clearance, % | 96.5 | 83.1 | 97.1 | 94.7 | 92.4 | 95.1 |
As can be seen from evaluation result, waste water COD has after treatment had obvious reduction, to the COD clearance of phenol wastewater all more than 90%.After continuous running 1000h, evaluation result lists in table 4.
Table 4 estimation of stability result
As can be seen from table 4 result, after catalyst uses 1000h, the catalyst activity using the inventive method to prepare does not change substantially, has good stability.
The present invention uses the noble metal with excellent catalytic activity as active component, add rare earth metal as auxiliary agent, rare earth metal and noble metal have good coordinative role, add the stability of catalyst and active and reduce cost, have good application prospect.
Claims (21)
1. a preparation method for catalytic wet oxidation catalyst, comprising:
(1) 150 order ~ 300 order active carbons are adopted amino acid process, then pull an oar;
(2) in amorphous alumina plastic process, introduce the active carbon slurries that step (1) obtains;
(3) material after the plastic that obtains of step (2) carries out aging, after hydrothermal treatment consists, refilters, washs, dry, obtains carrier material;
(4) carrier material of step (3) gained is made catalyst carrier;
(5) impregnated activated metal component and auxiliary agent in the catalyst carrier of step (4) gained, then dry, roasting under inert gas shielding, obtains catalytic wet oxidation catalyst.
2. in accordance with the method for claim 1, it is characterized in that the preparation of step (4) catalyst carrier at least adopts one of following method:
A, by the carrier material of step (3) gained, roasting under inert gas shielding, obtains catalyst carrier;
B, by shaping for the carrier material of step (3) gained, after drying, roasting under inert gas shielding, obtains catalyst carrier;
C, by carrier material roasting under inert gas shielding of step (3) gained, and then through shaping, after drying, roasting under inert gas shielding, obtains catalyst carrier.
3. in accordance with the method for claim 1, it is characterized in that in described catalyst, carrier be with 150 order ~ 300 object active carbons be core, with amorphous alumina for shell, wherein active carbon accounts for 10% ~ 70% of vehicle weight, and aluminium oxide accounts for 30% ~ 90% of vehicle weight.
4. in accordance with the method for claim 1, it is characterized in that described rare earth metal is one or more in lanthanum, cerium, praseodymium, neodymium.
5. in accordance with the method for claim 1, it is characterized in that, in described catalyst, active carbon accounts for 30% ~ 70% of vehicle weight, aluminium oxide accounts for 30% ~ 70% of vehicle weight.
6. in accordance with the method for claim 1, it is characterized in that in described catalyst, with the weight of catalyst for benchmark, the content of noble metal counts 0.01% ~ 1% with element, and the content of rare earth metal counts 1% ~ 15% with element.
7. in accordance with the method for claim 1, it is characterized in that described catalyst or powder catalyst, or preformed catalyst, the granularity of powder catalyst is 0.05 ~ 0.2mm, and preformed catalyst granularity is 0.5 ~ 8.0mm.
8. in accordance with the method for claim 1, it is characterized in that the character of step (1) described active carbon is as follows: specific area 500 ~ 3000m
2/ g, pore volume 0.5 ~ 1.8cm
3/ g, average pore radius 1 ~ 10nm.
9. in accordance with the method for claim 1, the active carbon making beating that it is characterized in that described in step (1) adopt add water, one or more in low-carbon alcohols pull an oar, wherein low-carbon alcohols to be carbon number be in the monohydric alcohol of 1 ~ 5 one or more.
10. in accordance with the method for claim 1, it is characterized in that the active carbon described in step (1) first adopts amino acid process, then pull an oar, described amino acid to be carbon number be less than 20 amino acid.
11. in accordance with the method for claim 1, it is characterized in that described amino acid consumption accounts for 2% ~ 50% of activated carbon weight.
12. in accordance with the method for claim 1, it is characterized in that described amino acid consumption accounts for 5% ~ 20% of activated carbon weight.
13. in accordance with the method for claim 1, it is characterized in that described amino acid is one or more in glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid.
14. in accordance with the method for claim 1, it is characterized in that: amino acid process active carbon is directly mixed with active carbon by amino acid, or amino acid is dissolved in solvent and adds active carbon again, solvent is wherein water, carbon number is one or more in the monohydric alcohol of 1 ~ 5; During amino acid process active carbon, its liquid-solid volume ratio is below 10.
15. in accordance with the method for claim 1, it is characterized in that: the plastic process of the amorphous alumina described in step (2) is the neutralization reaction process of acid material and alkaline material, plastic process adopts the mode of the continuous acid-base titration of soda acid, or adopts two kinds of materials and the mode of stream neutralization.
16. in accordance with the method for claim 1, it is characterized in that: in step (2), the incorporation way of the mixture of step (1) gained adopts the one or more combination of following manner: this mixture, in plastic neutralization reaction process, adds in plastic cans by (1) continuously; (2) this mixture is first joined in plastic cans, then will prepare in the acid material of amorphous alumina and alkaline material and plastic; (3) one or more with plastic material of this mixture are mixed, then in plastic material and plastic.
17. in accordance with the method for claim 1, it is characterized in that in step (3), before hydrothermal treatment consists, after filtration or heating concentration to liquid-solid ratio 2 ~ 5; Described heating simmer down to is heating steps (2) products obtained therefrom at 90 ~ 110 DEG C.
18. in accordance with the method for claim 1, it is characterized in that in step (3), described hydrothermal treatment consists is carried out in closed container, the temperature of hydrothermal treatment consists is 90 ~ 300 DEG C, described hydrothermal treatment consists is carried out under the pressure condition of self that produces when material treatment temperature, and described hydrothermal conditions is 0.5 ~ 48h.
19. in accordance with the method for claim 7, it is characterized in that: in step (3), described drying condition is as follows: drying 1 ~ 15 hour at 50 ~ 150 DEG C.
20. in accordance with the method for claim 2, it is characterized in that: in step (4), roasting condition described in method A is as follows: sintering temperature is 450 ~ 700 DEG C, roasting time is 1 ~ 10 hour, drying condition described in method B is at 80 ~ 200 DEG C, dry 1 ~ 15 hour, sintering temperature is 450 ~ 700 DEG C, roasting time is 1 ~ 10 hour, in method C, by carrier material roasting under inert gas shielding of step (3) gained, described roasting condition is as follows: sintering temperature is 450 ~ 700 DEG C, roasting time is 1 ~ 10 hour, and then through shaping, after drying, roasting under inert gas shielding, obtain catalyst carrier, drying condition after shaping is as follows: at 80 ~ 200 DEG C, dry 1 ~ 15 hour, roasting condition is as follows: sintering temperature is 450 ~ 700 DEG C, roasting time is 1 ~ 10 hour.
21. in accordance with the method for claim 1, it is characterized in that: in step (5), after catalyst soakage, and drying condition is at 80 ~ 200 DEG C, and dry 1 ~ 15 hour, sintering temperature condition was 450 ~ 700 DEG C of roastings 1 ~ 10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310620794.7A CN104667916B (en) | 2013-11-29 | 2013-11-29 | Method for preparing catalytic wet oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310620794.7A CN104667916B (en) | 2013-11-29 | 2013-11-29 | Method for preparing catalytic wet oxidation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104667916A true CN104667916A (en) | 2015-06-03 |
| CN104667916B CN104667916B (en) | 2017-05-17 |
Family
ID=53303814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310620794.7A Active CN104667916B (en) | 2013-11-29 | 2013-11-29 | Method for preparing catalytic wet oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104667916B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107398270A (en) * | 2016-05-18 | 2017-11-28 | 中国石油化工股份有限公司 | Wet oxidizing catalyst |
| CN107661764A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661765A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661762A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661770A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661769A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661759A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661766A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661763A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661767A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661771A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661760A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661761A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661768A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327454B (en) * | 2008-07-29 | 2010-09-15 | 华东理工大学 | Modified carbon-coated alumina supporter with nucleocapsid structure and preparation method thereof |
| CN101549289B (en) * | 2009-05-12 | 2012-08-22 | 武汉大学 | Nucleocapsid energizing agent for propelling agent and method for preparing same |
| CN101862684B (en) * | 2010-05-07 | 2012-07-04 | 大连理工大学 | Aluminum oxide-activated carbon composite carrier, preparation method and prepared catalyst |
-
2013
- 2013-11-29 CN CN201310620794.7A patent/CN104667916B/en active Active
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107398270A (en) * | 2016-05-18 | 2017-11-28 | 中国石油化工股份有限公司 | Wet oxidizing catalyst |
| CN107661764A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661765A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661762A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661770A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661769A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661759A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661766A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661763A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661767A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661771A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661760A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661761A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661768A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material |
| CN107661769B (en) * | 2016-07-27 | 2020-06-12 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661759B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661760B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661761B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104667916B (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104667916B (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN105618066A (en) | Catalytic wet oxidation catalyst and preparation method thereof | |
| CN104667985B (en) | A kind of catalytic wet oxidation catalyst and preparation method thereof | |
| CN104667935A (en) | Catalytic wet oxidation catalyst and preparation method thereof | |
| CN104667973A (en) | Catalyst carrier material and preparation method thereof | |
| CN104667922B (en) | Method for preparing noble metal catalyst for catalytic wet oxidation | |
| CN105709737A (en) | Catalytic wet oxidation catalyst and preparation method thereof | |
| CN104667936A (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN105709744A (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN104667917B (en) | Method for preparing catalytic wet oxidation noble metal catalyst | |
| CN105709732A (en) | Noble metal catalyst for catalytic wet oxidation and preparation method thereof | |
| CN105709776B (en) | The preparation method of catalytic wet oxidation catalyst | |
| CN105618040B (en) | A kind of preparation method of noble metal catalyst for CWO | |
| CN104667939A (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN104667933A (en) | Method for preparing wet oxidation catalyst | |
| CN104667920B (en) | Noble metal catalyst for catalytic wet oxidation and preparation method thereof | |
| CN104667919B (en) | The method for preparing catalytic wet oxidation catalyst | |
| CN104667934B (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN104667937B (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN104667923B (en) | Method for preparing noble metal catalyst for catalytic wet oxidation | |
| CN104667994A (en) | Method for preparing catalytic wet oxidation catalyst carrier | |
| CN105618041A (en) | Preparation method of precious metal catalyst used for catalytic wet oxidation | |
| CN104667991A (en) | Method for preparing catalytic wet oxidation catalyst carrier | |
| CN104667938A (en) | Method for preparing wet oxidation catalyst | |
| CN105709733A (en) | Noble metal catalyst for catalytic wet oxidation 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |