CN110252284A - A kind of forming method of catalytic wet oxidation catalyst - Google Patents
A kind of forming method of catalytic wet oxidation catalyst Download PDFInfo
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- CN110252284A CN110252284A CN201910474959.1A CN201910474959A CN110252284A CN 110252284 A CN110252284 A CN 110252284A CN 201910474959 A CN201910474959 A CN 201910474959A CN 110252284 A CN110252284 A CN 110252284A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
A kind of forming method of catalytic wet oxidation catalyst, belongs to technical field of waste water processing.It just can apply to the various powder catalyst industrialized in reactors including that need to be formed, it is characterized in that, the powder catalyst is transition metal system powder catalyst, forming process first adds additional adhesive, extrusion aid, pore structure modifying agent, is then mixed, mediated while is added dropwise binder, extrusion molding, drying, calcination steps；The present invention makees binder, nanometer ZrO by adding silica solution2, nano-TiO2Make additional adhesive, while reaching the requirement of mechanical strength of Catalystization application, the hydrothermal stability of catalyst can be effectively improved；Molding front and back catalyst activity is almost the same, good to the COD removal effect of waste water.
Description
Technical field
The present invention relates to a kind of forming methods of catalytic wet oxidation catalyst, belong to waste water treatment applications technical field.
Background technique
Catalytic wet air oxidation (CWAO) is a kind of processing high concentration, the common method of organic wastewater with difficult degradation thereby, this method
Using air or O2Organic matter can be thoroughly degraded to CO under the action of catalyst for oxidant2And H2O is one clean
Process route.Due to the advantages that its energy consumption of reaction is moderate, occupation area of equipment is small, the reaction time is short, pollutant process is thorough, closely
Extensive concern over year by industry.
The key technology of catalytic wet air oxidation is the research of catalyst.Domestic and international most common wastewater treatment is urged
Agent mainly includes three categories: noble metal system (such as Ru, Pt, Pd), Cu system, Rare Earth (such as Mn, Ce, Fe), these three types are urged
Agent respectively has advantage and disadvantage.But for solid catalyst, no matter preparing in any method, all need to be applied to through overmolding each
In kind industrialization reactor, molding is the essential process of Catalystization.
At present to the research relative maturity of shaping of catalyst method, treatment catalyst forming method is with extrusion molding and pressure
Based on sheetmolding.But which kind of method no matter is taken, finally requires to mention under the premise of meeting catalyst activity, mechanical strength
The service life of high catalyst.CN106693968A discloses a kind of method of composite catalyst extrusion molding, and this method is
Clay is added in powder catalyst or boehmite makees binder, is mainly used under conditions of 20-80 DEG C of reaction temperature,
Since reaction condition is mild, catalyst service life with higher.But it in the reaction of actual catalytic wet oxidation, urges
Agent will not only undergo the water environment of high temperature and pressure, will also be subjected to the corrosion of intermediate product small molecular organic acid, above-mentioned patent institute
The molding adhesives such as boehmite, the clay stated can not show good hydro-thermal under the reaction condition of this harshness
Stability.If preformed catalyst hydrothermal stability is poor, will part pulp during the reaction, after on the one hand will cause processing
On the other hand the secondary pollution of water also results in line clogging and reaction is caused to stop.Therefore, catalytic wet oxidation catalyst is improved
The key of service life is to improve the hydrothermal stability of catalyst.
For these problems, existing patent makees catalyst, patent announcement using the carrier of good hydrothermal stability by attempting
Number: CN 103157517B " TiZrO2Carrier and noble metal/TiZrO2Catalyst and its preparation and application " and CN102451680B
" wet oxidizing catalyst of composite oxide modified and preparation method thereof " individually discloses a kind of TiO2、ZrO2Shaping carrier,
TiO2、SiO2、Al2O3Shaping carrier, the preparation method of the preformed catalyst of carried noble metal Ru, this method first to carrier into
Row extrusion molding, then noble metal Ru is supported on carrier using infusion process, the catalyst of this method preparation has for high concentration
Machine wastewater treatment also shows good high-temperature hydrothermal stability.But precious metal raw material is not used only in this method, and needs to carry
The complexity preparation procedure such as body formed catalyst and activity component impregnation.
In addition, existing catalyst is after forming, it is right due to the type of binder and various additives, the difference of additive amount
Specific surface area, pore volume and the heap density of preformed catalyst can all cause a degree of change, to cause catalyst living
The decline of property, influences preformed catalyst to the COD removal effect of waste water.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the present invention provides a kind of forming method of catalytic wet oxidation catalyst, should
Method molding catalyst be mainly no adhesion material, especially transition metal oxide itself is difficult to form, lead to
It crosses addition silica solution and makees binder, nanometer ZrO2, nano-TiO2Make additional adhesive, further increase the mechanical strength of catalyst,
To reach the requirement of mechanical strength of Catalystization application, therefore it can effectively improve the hydrothermal stability of catalyst,
Catalyst preparation process can be simplified again, the molding of most powder catalyst is applicable in；Molding front and back catalyst activity base
This is consistent, good to the COD removal effect of waste water.
Above-mentioned goal of the invention is achieved through the following technical solutions: a kind of molding side of catalytic wet oxidation catalyst
Method is characterized by, the powder including the powder catalyst that need to could be applied to through overmolding in various industrialization reactors
Body catalyst forming process first adds additional adhesive, extrusion aid, pore structure modifying agent, is then mixed, is mediated while is added dropwise
Binder, extrusion molding, drying, calcination steps；
The powder catalyst is transition metal system powder catalyst, its parts by weight of transition metal system powder catalyst are 80
~ 150 parts；
The additional adhesive is nanometer ZrO2、TiO2One or both of, addition parts by weight are 15 ~ 75 parts；
The extrusion aid is one or both of sesbania powder, starch, adds 1.5 ~ 7.5 parts of parts by weight；
The pore structure modifying agent is one or both of oxalic acid, citric acid, and addition parts by weight are 3 ~ 15 parts；
The binder is silica aqueous solution；It is 100 ~ 130 parts that parts by weight, which are added dropwise, in it；
Preferably, the roasting using temperature programming control, heating rate be 2 ~ 5 DEG C/min, maturing temperature be 300 ~
600 DEG C, calcining time is 2 ~ 5 hours.
Preferably, the transition metal system powder catalyst is by grinding to the hidden manganese potassium of 100 ~ 150 purposes
Mine (OMS-2) powder, parts by weight are 80 ~ 100 parts；
The additional adhesive is nanometer ZrO2Powder adds 15 ~ 25 parts of parts by weight；
The extrusion aid is sesbania powder, and addition parts by weight are 1.5 ~ 2 parts；
The pore structure modifying agent is citric acid, and addition parts by weight are 3 ~ 4 parts；
The binder is silica aqueous solution；It is 100 ~ 120 parts that parts by weight, which are added dropwise, in it；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 18 ~ 22 min, is added dropwise when mediating
The adhesive silicon sol aqueous solution of 25% ~ 35% content；Continue 18 ~ 22 min of kneading after being added dropwise, until material is at plastic character
State；The material finished will be mediated to be added in extruder, control 20 ~ 30 rad/min of extruder double-screw revolving speed, extrusion pressure 80 ~
120 kg；The catalyst of extrusion molding is put into air dry oven dry；Catalyst after drying is roasted, roasting is adopted
It is controlled with temperature programming, heating rate is 2 ~ 5 DEG C/min, and maturing temperature is 300 ~ 450 DEG C, and calcining time is 2 ~ 3 hours.
Preferably, the transition metal system powder catalyst is by grinding to the industry of 100 ~ 150 mesh
MnO2Powder, parts by weight are 130 ~ 150 parts；
The additional adhesive is nano-TiO2Powder adds 70 ~ 80 parts of parts by weight；
The extrusion aid is starch, and addition parts by weight are 6.5 ~ 7.5 parts；
The pore structure modifying agent is oxalic acid, and addition parts by weight are 13 ~ 15 parts；
The binder is silica aqueous solution；It is 110 ~ 120 parts that parts by weight, which are added dropwise, in it；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 28 ~ 32 min, is added dropwise when mediating
The adhesive silicon sol aqueous solution of 25% ~ 35% content；Continue 18 ~ 22 min of kneading after being added dropwise, until material is at plastic character
State；The material finished will be mediated to be added in extruder, control 25 ~ 35 rad/min of extruder double-screw revolving speed, extrusion pressure 90 ~
110 kg；The catalyst of extrusion molding is put into air dry oven dry；Catalyst after drying is roasted, roasting is adopted
It is controlled with temperature programming, heating rate is 2 ~ 5 DEG C/min, and maturing temperature is 450 ~ 600 DEG C, and calcining time is 3 ~ 5 hours.
Preferably, the transition metal system powder catalyst is by grinding to the manganese sand filtration of 100 ~ 150 mesh
Feed powder body, parts by weight are 100 ~ 120 parts；
The additional adhesive is nano-TiO2Powder adds 30 ~ 40 parts of parts by weight；
The extrusion aid is starch, and addition parts by weight are 3 ~ 4 parts；
The pore structure modifying agent is oxalic acid, and addition parts by weight are 6 ~ 8 parts；
The binder is silica aqueous solution；It is 100 ~ 110 parts that parts by weight, which are added dropwise, in it；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 28 ~ 32 min, is added dropwise when mediating
The adhesive silicon sol aqueous solution of 28% ~ 32% content；Continue 18 ~ 22 min of kneading after addition, until material is at plastic character
State；The material finished will be mediated to be added in extruder, control 28 ~ 32 rad/min of extruder double-screw revolving speed, extrusion pressure 100
~120 kg；The catalyst of extrusion molding is put into air dry oven dry；Catalyst after drying is roasted, is roasted
It is controlled using temperature programming, heating rate is 2 ~ 5 DEG C/min, and maturing temperature is 400 ~ 500 DEG C, and calcining time is 2 ~ 5 hours.
Preferably, the transition metal system powder catalyst is by grinding to the hydrotalcite of 100 ~ 150 mesh
The Cu series catalysts powder of load, parts by weight are 130 ~ 150 parts；
The additional adhesive is nanometer ZrO2Powder adds 50 ~ 65 parts of parts by weight；
The extrusion aid is sesbania powder, and addition parts by weight are 6 ~ 7 parts；
The pore structure modifying agent is citric acid, and addition parts by weight are 12 ~ 14 parts；
The binder is silica aqueous solution；It is 120 ~ 130 parts that parts by weight, which are added dropwise, in it；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 18 ~ 22 min, is added dropwise when mediating
The adhesive silicon sol aqueous solution of 28% ~ 32% content；Continue 18 ~ 22 min of kneading after being added dropwise, until material is at plastic character
State；The material finished will be mediated to be added in extruder, control 25 ~ 35 rad/min of extruder double-screw revolving speed, extrusion pressure 70 ~
90 kg；The catalyst of extrusion molding is put into air dry oven dry；Catalyst after drying is roasted, roasting is adopted
It is controlled with temperature programming, heating rate is 2 ~ 5 DEG C/min, and maturing temperature is 300 ~ 400 DEG C, and calcining time is 3 ~ 4 hours.
Beneficial effects of the present invention:
(1) extrusion molding catalyst prepared by the present invention is used, mechanical strength meets industrializeding catalyst and wants to mechanical strength
It asks.
(2) SiO is used2That is silica solution, nano-TiO2, nanometer ZrO2Acidproof, high corrosion resistance nano material bonds
Agent and additional adhesive, high temperature, high pressure thermal and hydric environment under the hydrothermal stability of catalyst can be greatly improved.
(3) catalyst described in is mainly used for high concentrated organic wastewater processing, 220 ~ 280 DEG C of reaction temperature, pressure 5 ~ 8
MPa, molding front and back catalyst activity is almost the same, good to the COD removal effect of waste water.
(4) this method provides a kind of more general side for the molding of most of catalytic wet oxidation powder catalyst
Method, especially the molding biggish material of difficulty, have good industrial applications prospect.
Detailed description of the invention
Fig. 1 is the body formed front and back catalytic activity comparison of catalyst powder that the embodiment of the present invention 1 provides；
Fig. 2 is the preformed catalyst successive reaction catalytically active assessment that the embodiment of the present invention 2 provides；
Fig. 3 is the preformed catalyst reaction front and back mechanical strength evaluation that the embodiment of the present invention 2 provides；
Specific implementation method
1-5 the invention will be further described by the following examples:
Embodiment 1: a kind of forming method of catalytic wet oxidation catalyst, i.e., the forming method of hidden cryptomelane (OMS-2) powder,
The transition metal system powder catalyst be by grinding to the hidden cryptomelane of 100 ~ 150 purposes (OMS-2) powder, it is heavy
Measure 0.8 kg；
The additional adhesive is nanometer ZrO2Powder, 0.16 kg of weight；
The extrusion aid is sesbania powder, 0.016 kg of weight；
The pore structure modifying agent is citric acid, 0.032 kg of weight；
The binder is silica aqueous solution, and 1.0 kg of weight is added dropwise；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 20 min, be added dropwise 30% when mediating and contain
The adhesive silicon sol aqueous solution of amount continues to mediate 20 min after being added dropwise, until material is at plastic state；Kneading is finished
Material be added extruder in, control 30 rad/min of extruder double-screw revolving speed, 80 kg of extrusion pressure；Extrusion cavities board mold
For cylinder, 2.5 mm of diameter.The catalyst of extrusion molding is put into drying in air dry oven, takes temperature-controlled drying step by step,
Each drying 2 hours at 40 DEG C, 60 DEG C, 80 DEG C respectively；Catalyst after drying is roasted, roasting uses program liter
Temperature control system, heating rate are 2 DEG C/min, and maturing temperature is 300 DEG C, and calcining time is 3 hours.
Mechanical strength evaluation: the catalyst after roasting is evaluated under catalyst strength tester, is tested 150 times and is taken
Average value, 122 N/cm of catalyst average mechanical strength.
Catalytically active assessment: being dyeing waste water with the catalyst treatment industrial organic waste water that above-described embodiment method obtains,
Its COD is 4225 mg/L, pH 7.It is evaluated, 280 DEG C of reaction temperature, 8.0 MPa of pressure, is reacted using batch reactor
2 h of time, forming hidden cryptomelane (OMS-2) catalyst COD removal rate is 97.5%, without molding hidden cryptomelane (OMS-2) powder
Body catalyst COD removal rate is 98.9%, therefore ten parts of catalyst activity reduction limited.
Embodiment 2: a kind of forming method of catalytic wet oxidation catalyst, i.e., the molding of hidden cryptomelane (OMS-2) powder
Method, the transition metal system powder catalyst are by grinding to the hidden cryptomelane of 100 ~ 150 purposes (OMS-2) powder
Body, 0.8 kg of weight；
The additional adhesive is nanometer ZrO2Powder, 0.24 kg of weight；
The extrusion aid is sesbania powder, 0.016 kg of weight；
The pore structure modifying agent is citric acid, 0.032 kg of weight；
The binder is silica aqueous solution, and 1.2 kg of weight is added dropwise；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 30 min, 30% is added dropwise when mediating and contains
The adhesive silicon sol aqueous solution of amount continues to mediate 20 min after being added dropwise, until material is at plastic state；Kneading is finished
Material be added extruder in, control 25 rad/min of extruder double-screw revolving speed, 120 kg of extrusion pressure；Extrusion cavities board mold
For cylinder, 3.0 mm of diameter.The catalyst of extrusion molding is put into drying in air dry oven, takes temperature-controlled drying step by step,
Each drying 2 hours at 40 DEG C, 60 DEG C, 80 DEG C respectively；Catalyst after drying is roasted, roasting uses program liter
Temperature control system, heating rate are 2 DEG C/min, and maturing temperature is 450 DEG C, and calcining time is 2 hours.
Mechanical strength evaluation: the catalyst after roasting is evaluated under catalyst strength tester, is tested 100 times and is taken
Average value, 138 N/cm of catalyst average mechanical strength.
Catalytically active assessment: being dyeing waste water with the catalyst treatment industrial organic waste water that above-described embodiment method obtains,
Its COD is 3500 mg/L, pH 6.7.It is evaluated using fixed-bed reactor, 280 DEG C of reaction temperature, pressure 8.0
MPa, 1.0 h of air speed-1, react runing time 432 hours, forming hidden cryptomelane (OMS-2) catalyst COD average removal rate is
96.3%。
Mechanical strength is evaluated after reaction: the catalyst detergent after reaction being dried, catalyst strength evaluation, test are carried out
It is averaged for 100 times, 121 N/cm of catalyst average mechanical strength.
Embodiment 3:
A kind of forming method of catalytic wet oxidation catalyst, i.e., a kind of industry MnO2The forming method of powder, the transition
Metal system powder catalyst is by grinding to the industrial MnO of 100 ~ 150 mesh2Powder,
It is a kind of more difficult molding material.1.5 kg of its weight；
The additional adhesive is nano-TiO2Powder, 0.75 kg of weight；
The extrusion aid is starch, 0.075 kg of weight；
The pore structure modifying agent is oxalic acid, 0.15 kg of weight；
The binder is silica aqueous solution, and 1.2 kg of weight is added dropwise；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 30 min, 30% is added dropwise when mediating and contains
The adhesive silicon sol aqueous solution of amount continues to mediate 20 min after being added dropwise, until material is at plastic state；Kneading is finished
Material be added extruder in, control 30 rad/min of extruder double-screw revolving speed, 100 kg of extrusion pressure；Extrusion cavities board mold
For cylinder, 2.5 mm of diameter.The catalyst of extrusion molding is put into drying in air dry oven, takes temperature-controlled drying step by step,
Each drying 2 hours at 40 DEG C, 60 DEG C, 80 DEG C respectively；Catalyst after drying is placed in air atmosphere at 600 DEG C and is roasted
It burns 4 hours, roasting process takes Temperature Programmed Processes, 5 DEG C/min of heating rate.
Mechanical strength evaluation: the catalyst after roasting is evaluated under catalyst strength tester, is tested 150 times and is taken
Average value, 86 N/cm of catalyst average mechanical strength.
Catalytically active assessment: being evaluated using fixed-bed reactor, and industrial organic waste water is dyeing waste water, COD
For 3780 mg/L, pH 6.5.220 DEG C of reaction temperature, 5 MPa of pressure, 1.5 h of air speed-1, it reacts runing time 300 hours,
COD average removal rate is 74%.
Embodiment 4:
A kind of forming method of catalytic wet oxidation catalyst, i.e., a kind of forming method of manganese sand filtering material powder, the transition
Metal system powder catalyst is by grinding to the manganese sand filtering material powder of 100 ~ 150 mesh, is a kind of more difficult molding containing work
Industry MnO2The water treatment filter material of content 35% ~ 45%.1.0 kg of its weight；
The additional adhesive is nano-TiO2Powder, 0.3 kg of weight；
The extrusion aid is starch, 0.03 kg of weight；
The pore structure modifying agent is oxalic acid, 0.06 kg of weight；
The binder is silica aqueous solution, and 1.0 kg of weight is added dropwise；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 30 min, 30% is added dropwise when mediating and contains
The adhesive silicon sol aqueous solution of amount continues to mediate 20 min after being added dropwise, until material is at plastic state；Kneading is finished
Material be added extruder in, control 28 rad/min of extruder double-screw revolving speed, 120 kg of extrusion pressure；Extrusion cavities board mold
For cylinder, 2.5 mm of diameter.The catalyst of extrusion molding is put into drying in air dry oven, takes temperature-controlled drying step by step,
Each drying 2 hours at 40 DEG C, 60 DEG C, 80 DEG C respectively.Catalyst after drying is placed in air atmosphere at 400 DEG C and is roasted
It burns 2 hours, roasting process takes Temperature Programmed Processes, 5 DEG C/min of heating rate.
Mechanical strength evaluation: the catalyst after roasting is evaluated under catalyst strength tester, is tested 100 times and is taken
Average value, 102 N/cm of catalyst average mechanical strength.
Catalytically active assessment: being evaluated using fixed-bed reactor, and industrial organic waste water is dyeing waste water, COD
For 5000 mg/L, pH 6.8.250 DEG C of reaction temperature, 6.5 MPa of pressure, 1.5 h of air speed-1, it is small to react runing time 290
When, COD average removal rate is 84%.
Embodiment 5:
A kind of forming method of catalytic wet oxidation catalyst, i.e., a kind of molding side of the Cu series catalysts powder of hydrotalcite load
Method, the transition metal system powder catalyst are by grinding to the Cu system catalysis of the hydrotalcite load of 100 ~ 150 mesh
Agent powder is a kind of powder material of more difficult molding clay property, 1.5 kg of weight；
The additional adhesive is nanometer ZrO2Powder, 0.65 kg of weight；
The extrusion aid is sesbania powder, 0.07 kg of weight；
The pore structure modifying agent is citric acid, 0.14 kg of weight；
The binder is silica aqueous solution, and 1.25 kg of weight is added dropwise;
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 20 min, 30% is added dropwise when mediating and contains
The adhesive silicon sol aqueous solution of amount continues to mediate 20 min after being added dropwise, until material is at plastic state；Kneading is finished
Material be added extruder in, control 30 rad/min of extruder double-screw revolving speed, 80 kg of extrusion pressure；Extrusion cavities board mold
For cylinder, 3.0 mm of diameter.
The catalyst feed of extrusion molding is put into drying in air dry oven, temperature-controlled drying step by step is taken, respectively 40
DEG C, 60 DEG C, each drying 2 hours at 80 DEG C.
Catalyst after drying is placed in air atmosphere at 350 DEG C and is roasted 3 hours, roasting process takes temperature programming
Process, 2 DEG C/min of heating rate.
Mechanical strength evaluation: the catalyst after roasting is evaluated under catalyst strength tester, is tested 100 times and is taken
Average value, 162 N/cm of catalyst average mechanical strength.
Catalytically active assessment: being evaluated using fixed-bed reactor, and industrial organic waste water is dyeing waste water, COD
For 4470 mg/L, pH 6.5.280 DEG C of reaction temperature, 8.0 MPa of pressure, 1.0 h of air speed-1, it is small to react runing time 260
When, COD average removal rate is 94%.
Above although it have been described that 5 embodiments of the invention, but in the principle and objective for not departing from present patent application
In the case where a variety of change, modification, replacement and modification can be carried out to these embodiments, the protection scope of present patent application is by weighing
Benefit require and its equivalent replacement limited, without creative work improvements introduced should included in the application protection scope it
It is interior.
Claims (6)
1. a kind of forming method of catalytic wet oxidation catalyst, including need to could be applied to various industrialization through overmolding and react
Powder catalyst in device, which is characterized in that the powder shaping of catalyst process first add additional adhesive, extrusion aid,
Then pore structure modifying agent is mixed, is mediated while is added dropwise binder, extrusion molding, drying, calcination steps；
The powder catalyst is transition metal system powder catalyst, its parts by weight of transition metal system powder catalyst are 80
~ 150 parts；
The additional adhesive is nanometer ZrO2, nano-TiO2One or both of, addition parts by weight are 15 ~ 75 parts；
The extrusion aid is one or both of sesbania powder, starch, and addition parts by weight are 1.5 ~ 7.5 parts；
The pore structure modifying agent is one or both of citric acid, oxalic acid, and addition parts by weight are 3 ~ 15 parts；
The binder is silica aqueous solution；It is 100 ~ 130 parts that parts by weight, which are added dropwise, in it.
2. a kind of forming method of catalytic wet oxidation catalyst described in claim 1, which is characterized in that the roasting is adopted
It is controlled with temperature programming, heating rate is 2 ~ 5 DEG C/min, and maturing temperature is 300 ~ 600 DEG C, and calcining time is 2 ~ 5 hours.
3. a kind of forming method of catalytic wet oxidation catalyst as claimed in claim 2, which is characterized in that the transition gold
Category system powder catalyst be by grind to the hidden cryptomelane of 100 ~ 150 purposes ((OMS-2) powder, parts by weight are 80 ~
100 parts；
The additional adhesive is nanometer ZrO2Powder adds 15 ~ 25 parts of parts by weight；
The extrusion aid is sesbania powder, and addition parts by weight are 1.5 ~ 2 parts；
The pore structure modifying agent is citric acid, and addition parts by weight are 3 ~ 4 parts；
The binder is silica aqueous solution；It is 100 ~ 120 parts that parts by weight, which are added dropwise, in it；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 18 ~ 22 min, is added dropwise when mediating
The adhesive silicon sol aqueous solution of 25% ~ 35% content；Continue 18 ~ 22 min of kneading after being added dropwise, until material is at plastic character
State；The material finished will be mediated to be added in extruder, control 20 ~ 30 rad/min of extruder double-screw revolving speed, extrusion pressure 80 ~
120 kg；
The catalyst of extrusion molding is put into air dry oven dry；Catalyst after drying is roasted, roasting uses
Temperature programming control, heating rate are 2 ~ 5 DEG C/min, and maturing temperature is 300 ~ 450 DEG C, and calcining time is 2 ~ 3 hours.
4. a kind of forming method of catalytic wet oxidation catalyst as claimed in claim 2, which is characterized in that the transition gold
Category system powder catalyst is by grinding to the industrial MnO of 100 ~ 150 mesh2Powder, parts by weight are 130 ~ 150 parts；
The additional adhesive is nano-TiO2Powder adds 70 ~ 80 parts of parts by weight；
The extrusion aid is starch, and addition parts by weight are 6.5 ~ 7.5 parts；
The pore structure modifying agent is oxalic acid, and addition parts by weight are 13 ~ 15 parts；
The binder is silica aqueous solution；It is 110 ~ 120 parts that parts by weight, which are added dropwise, in it；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 28 ~ 32 min, is added dropwise when mediating
The adhesive silicon sol aqueous solution of 25% ~ 35% content；Continue 18 ~ 22 min of kneading after being added dropwise, until material is at plastic character
State；The material finished will be mediated to be added in extruder, control 25 ~ 35 rad/min of extruder double-screw revolving speed, extrusion pressure 90 ~
110 kg；The catalyst of extrusion molding is put into air dry oven dry；Catalyst after drying is roasted, is roasted
It is controlled using temperature programming, heating rate is 2 ~ 5 DEG C/min, and maturing temperature is 450 ~ 600 DEG C, and calcining time is 3 ~ 5 hours.
5. a kind of forming method of catalytic wet oxidation catalyst as claimed in claim 2, which is characterized in that the transition gold
Category system powder catalyst is by grinding to the manganese sand filtering material powder of 100 ~ 150 mesh, and parts by weight are 100 ~ 120 parts；
The additional adhesive is nano-TiO2Powder adds 30 ~ 40 parts of parts by weight；
The extrusion aid is starch, and addition parts by weight are 3 ~ 4 parts；
The pore structure modifying agent is oxalic acid, and addition parts by weight are 6 ~ 8 parts；
The binder is silica aqueous solution；It is 100 ~ 110 parts that parts by weight, which are added dropwise, in it；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 28 ~ 32 min, is added dropwise when mediating
The adhesive silicon sol aqueous solution of 28% ~ 32% content；Continue 18 ~ 22 min of kneading after addition, until material is at plastic character
State；The material finished will be mediated to be added in extruder, control 28 ~ 32 rad/min of extruder double-screw revolving speed, extrusion pressure 100
~120 kg；The catalyst of extrusion molding is put into air dry oven dry；Catalyst after drying is roasted, is roasted
It is controlled using temperature programming, heating rate is 2 ~ 5 DEG C/min, and maturing temperature is 400 ~ 500 DEG C, and calcining time is 2 ~ 5 hours.
6. a kind of forming method of catalytic wet oxidation catalyst as claimed in claim 2, which is characterized in that the transition gold
Category system powder catalyst is by grinding to the Cu series catalysts powder of the hydrotalcite load of 100 ~ 150 mesh, parts by weight
Number is 130 ~ 150 parts；
The additional adhesive is nanometer ZrO2Powder adds 50 ~ 65 parts of parts by weight；
The extrusion aid is sesbania powder, and addition parts by weight are 6 ~ 7 parts；
The pore structure modifying agent is citric acid, and addition parts by weight are 12 ~ 14 parts；
The binder is silica aqueous solution；It is 120 ~ 130 parts that parts by weight, which are added dropwise, in it；
The agitated machine of above-mentioned material is mixed, is added in kneader after mixing completely and mediates 18 ~ 22 min, is added dropwise when mediating
The adhesive silicon sol aqueous solution of 28% ~ 32% content；Continue 18 ~ 22 min of kneading after being added dropwise, until material is at plastic character
State；The material finished will be mediated to be added in extruder, control 25 ~ 35 rad/min of extruder double-screw revolving speed, extrusion pressure 70 ~
90 kg；The catalyst of extrusion molding is put into air dry oven dry；Catalyst after drying is roasted, roasting is adopted
It is controlled with temperature programming, heating rate is 2 ~ 5 DEG C/min, and maturing temperature is 300 ~ 400 DEG C, and calcining time is 3 ~ 4 hours.
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| CN115475619A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Wet oxidation catalyst and preparation method and application thereof |
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