CN109621944A - The method for preparing integral catalyzer using waste sill - Google Patents
The method for preparing integral catalyzer using waste sill Download PDFInfo
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- CN109621944A CN109621944A CN201811429647.0A CN201811429647A CN109621944A CN 109621944 A CN109621944 A CN 109621944A CN 201811429647 A CN201811429647 A CN 201811429647A CN 109621944 A CN109621944 A CN 109621944A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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Abstract
The present invention provides a kind of methods for preparing integral catalyzer using waste sill, it is the raw material for preparing integral catalyzer with waste base, it is broadly divided into activation and molding two parts during the preparation process, it is being no more than 200 DEG C of moldings that catalyst can be completed, it forms in rear catalyst and is connected based on ionic bond and covalent bond between substance, supplemented by hydrogen bond and Van der Waals force, there is good mechanical strength.Not only surface possesses good catalytic effect to the catalyst, and the active component when surface is after fall off, internal component also has good catalytic activity after being exposed, this not only adds the service lifes of catalyst, and compared to conventional catalyst, the use of the catalyst reduces catalyst change expense.The preparation method of monolithic catalyst of the present invention is novel, simple, efficient, at low cost, catalyst long service life, and intensity is high, and activity is good, and quality is high, is able to achieve changing rejected material to useful resource, environmental-friendly, has significant promotional value.
Description
Technical field
The present invention relates to a kind of preparation methods of integral catalyzer, further relate to a kind of changing rejected material to useful resource method, application
In catalyst preparation and applied technical field.
Background technique
Catalyst is that one kind can change reactant chemical reaction rate without changing chemical balance, catalysis in chemical reaction
Agent, which can improve, can also reduce reactant chemical reaction rate, and the quality of itself and chemical property all do not have before and after chemical reaction
There is the substance to change.According to statistics, there are about in 90% or more industrial process use catalyst, as chemical industry, petrochemical industry, biochemistry,
Environmental protection etc..Catalyst occupies extremely important status, the activity of catalyst in modern chemical industry, and selectivity and stability are
Measure the important indicator of catalyst performance, noble metal catalyst and transition-metal catalyst are with excellent activity, selectivity and steady
It is qualitative and by attention, be widely used in every field.Wherein, transition-metal catalyst catalytic activity is high, and persistence is good, at
This is low, is increasingly becoming catalyst field research emphasis.However, the use cost accounting of catalyst is still very in industrial processes
It is high.In order to change this status, it is applied in industry using the slag containing transition metal, clinker or tailing production catalyst,
On the one hand the added value that can be improved waste base, on the other hand can also reduce the production and application cost of catalyst.But
The technique is not mature enough, and secondary pollution can be generated during production or fully effective can not utilize waste base.
More for catalyst research at present and more mature is fine catalyst, and there are pressure drops for fine catalyst
Greatly, easily purging, the disadvantages of mechanical strength is small, especially for the flue gas containing flying dust, it is easy to cause catalyst bed to block,
Therefore in actual industrial utilization, integral catalyzer is all used, and integral catalyzer has irreplaceable advantage, example
Such as:
1. bed pressure drop is significant lower；
2. mass-transfer efficiency is significantly increased；
3. enlarge-effect is less obvious；
4. the separation of integral catalyzer and regeneration are relatively easy.
The integral catalyzer used in the market mainly has board-like, honeycomb and corrugated plating catalyst, these three catalyst
Good activity is suffered from, but still suffers from many problems in the technique of shaping of catalyst, such as:
1. prepare integral catalyzer using infusion process, active component is easy to fall off and load factor is not high；
2. prepare monolithic catalyst using the blending extrusion method of forming, catalyst core amounts of components is less economical greatly；
3. needing to be calcined in 1100 DEG C or more of high temperature to improve the machinery of catalyst during shaping of catalyst
Performance, and this will lead to the inactivation of the active component in catalyst, reduce the performance of catalyst.
Therefore, it is badly in need of finding a kind of new technical means, to solve current transition-metal catalyst production and use multiple
Problem, including the problem that catalyst production and application cost is excessively high, waste base prepares catalyst and leads to the problem of secondary pollution, with
And can shaping of catalyst indices meet the problem of industrial requirement.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The method for preparing integral catalyzer using waste sill is being no more than 200 DEG C of moldings that catalyst can be completed, after molding
Monolithic catalyst between substance connection have good based on ionic bond and covalent bond, supplemented by hydrogen bond and Van der Waals force
Mechanical strength.Not only surface possesses good catalytic effect to the catalyst, but also after the active component when surface falls off, internal
Component also has good catalytic activity after being exposed, and this not only adds the service lifes of catalyst, and compared to normal
Catalyst is advised, the use of the catalyst reduces catalyst change expense.The preparation method of the monolithic catalyst is novel, it is simple,
Efficiently, at low cost, catalyst long service life, intensity is high, and activity is good, and quality is high, is able to achieve changing rejected material to useful resource, environment friend
Good, energy saving carbon drop, environmental pollution control is of great significance, and has significant promotional value.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A method of integral catalyzer being prepared using waste sill, the waste sill has containing transition metal
Slag, clinker or slag, its step are as follows:
Step 1: waste sill is activated, steps are as follows for specific activation method:
A. compound concentration is the HNO of 1mol/L3The NaOH solution that solution and concentration are 1mol/L, it is spare；And take waste base
Material obtains waste original washing powder material by crushed 50 meshes, spare；
B. a certain amount of waste original washing powder material prepared in the step a is taken, addition is a certain amount of to match in the step a
The HNO made3Solution is mixed, waste original washing powder material and HNO3The ratio of solution mixing is (1~3) g:25mL, and stirring is at least
After 30min, a certain amount of prepared NaOH solution in the step a is added, controls solution 8~9 in pH, then stir
After mixing at least 30min, centrifuging and taking solid is spare；
C. the solid obtained in the step b is put into progress 5-8h drying process in the baking oven not higher than 100 DEG C, to
After solid is dry, solid transfer is placed in Muffle furnace, Muffle furnace temperature programming system is then started, is being not higher than 400 DEG C
Constant temperature under carry out at least 3h high-temperature process, then take out solid material, it is spare；
Step 2: being mixed with chemically bonded ceramics catalyst using waste base, monoblock type catalysis is obtained by moulding process
Agent, method and step are as follows:
(1) auxiliary exciting agent is prepared, according to K2O:Al2O3:SO3:H2The mass ratio of O is the ratio of 1:1.2:0.3:1.5, will be each
Drug is mixed, and is stirred evenly, and auxiliary exciting agent is obtained, spare；
(2) in addition take a certain amount of waste sill in the step 1 it is activated processing preparation solid material into
Row mixing, control mixing quality ratio be (2.3-3.1): 1, obtain mixed raw material, then according to mixed raw material total amount based on
Amount, be added relative to mixed raw material mass ratio be 5% CaO, be added relative to mixed raw material mass ratio for 3% in institute
The auxiliary exciting agent prepared in step (1) is stated, and the H for being 35% relative to the mass ratio of mixed raw material is added2O is mixed
It closes uniformly, prepares ball mill mixing, be then placed in ball mill progress ball milling at least 10min, then by the solid material after gained ball milling
Material, which is put into mold, to be formed；
(3) the mold at least 8h disposed within that will be put into the solid material after the step (2) ball milling is stood, during which every
It is spaced solid material surface of most 2h into mold and sprays a small amount of water, to keep solid material wet；
(4) by the step (3) mold and solid material be put into tube furnace together, water is passed through into tube furnace
Steam, control vapor flow are not higher than 0.2ml/min, start tube furnace temperature programming system, are carrying out extremely not higher than 200 DEG C
Few 22h constant temperature processing；
(5) after to the constant temperature processing routine of the step (4), continue to be passed through vapor into tube furnace, and control
Flow is not higher than 0.1ml/min, and the time that control is passed through vapor is 2-3h, is post-processed；
(6) after the post-processing of the step (4), mold and solid material is taken out from tube furnace, makes mould at room temperature
Tool and solid material are dried, and after to be dried, are demoulded to solid material to get integral catalyzer is arrived.
Waste sill as currently preferred technical solution, in the step 1, for being used in activation process
Constituent mass content are as follows: levels of transition metals 8-15%, SiO2For 30-42%, Al2O3For 12-20%, K2O≤1.3%,
MgO≤0.8%.The best composition mass content of waste sill for being used in activation process are as follows: the content of transition metal
For 10%, SiO2For 35%, Al2O3For 12%, K2O is 0.8%, MgO 0.5%.
Other waste as currently preferred technical solution, in the step 2, for being used in forming process
Sill constituent mass content are as follows: SiO2For 25-33%, Al2O3For 9-17%, CaO 38-48%, SO3≤ 2%.For at
The best composition mass content of the other waste sill used during type are as follows: SiO2For 28%, Al2O3For 15%, CaO
For 40%, SO3It is 1.5%.
As currently preferred technical solution, in the step 2, the axial compression resistance of prepared integral catalyzer
Intensity is 220-280N/cm2, radial crushing strength 80-100N/cm2, wear strength 0.080-0.10%/kg；
The fine cracks quantity of the unilateral end face of the integral catalyzer of preparation is at 3-7, and its crackle Kuan Du≤0.040mm is split
Line length is the 25-33% of catalyst total length.
As currently preferred technical solution, in the step 2, prepared integral catalyzer surface forms and urges
Agent active layer, after the active component on integral catalyzer surface in use falls off, inside integral catalyzer
Component can be exposed, and form mesoporous type catalytic activity interface.
As currently preferred technical solution, in the step 2, substance in prepared integral catalyzer material
Between connection based on ionic bond and covalent bond, supplemented by hydrogen bond and Van der Waals force.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the method for the present invention is prepared compared to the preparation of traditional preformed catalyst, catalyst of the present invention using waste base, give up
Object base is mainly derived from slag, clinker etc., and is broadly divided into activation and molding two parts step, and the catalyst system can be completed
Standby, method is simple, it is easy to accomplish, preparation cost is low, easily controllable；
2. the method for the present invention is 1100 DEG C or more compared to general shaping of catalyst calcination temperature, the present invention prepares catalysis
Being molded under 200 DEG C of cryogenic conditions for agent can be completed, and connection is based on ionic bond and covalent bond between substance in material, hydrogen bond
Supplemented by Van der Waals force, therefore possess good mechanical strength.
3. compared to the use of general preformed catalyst, the integral catalyzer prepared using the method for the present invention not only surface
Possess good catalytic effect, and after the active component when surface falls off, internal component also has good after being exposed
Catalytic activity, this not only adds the service lifes of catalyst, and compared to conventional catalyst, and the use of the catalyst is dropped
Low catalyst change expense.
Detailed description of the invention
Fig. 1 is the process flow chart for the method that the embodiment of the present invention one prepares integral catalyzer using waste sill.
Specific embodiment
It is illustrated below in conjunction with specific embodiment, details are as follows for the preferred embodiment of the present invention:
Embodiment one
In the present embodiment, referring to Fig. 1, a method of integral catalyzer being prepared using waste sill, with manganese ore
Slag, flyash and plasma glass slag are the raw material for preparing integral catalyzer, and its step are as follows:
Step 1: waste sill is activated, steps are as follows for specific activation method:
A. compound concentration is the HNO of 1mol/L3The NaOH solution that solution and concentration are 1mol/L, it is spare；And manganese mud is taken,
By crushed 50 meshes, manganese mud waste original washing powder material is obtained, it is spare；
B. the manganese mud waste original washing powder material for taking 3g to prepare in the step a is added 25ml and prepares in the step a
HNO3Solution is mixed, and after stirring 30min, is added a certain amount of prepared NaOH solution in the step a, is made
Solution is controlled in pH 8~8.5, and after being stirred for 30min, centrifuging and taking solid is spare；
C. the solid obtained in the step b is put into progress 8h drying process in 100 DEG C of baking oven, it is dry to solid
Afterwards, solid transfer is placed in Muffle furnace, then starts Muffle furnace temperature programming system, 3h is carried out under 400 DEG C of constant temperature
High-temperature process then takes out solid material, spare；
Step 2: being mixed with chemically bonded ceramics catalyst using waste base, monoblock type catalysis is obtained by moulding process
Agent, method and step are as follows:
(1) auxiliary exciting agent is prepared, according to mass ratio K2O:Al2O3:SO3:H2O=1:1.2:0.3:1.5 carries out each drug
Mixing, and stir evenly, auxiliary exciting agent is obtained, it is spare；
(2) 3g flyash, 2.5g plasma glass slag and the 1.77g activated processing in the step 1 are in addition taken
The solid material of preparation is mixed, and mixed raw material is obtained, and then according to measuring based on mixed raw material total amount, is added relative to mixed
The CaO that the mass ratio of raw material is 5% is closed, the preparation in the step (1) for being 3% relative to the mass ratio of mixed raw material is added
Auxiliary exciting agent, and be added relative to mixed raw material mass ratio be 35% H2O, is carried out uniformly mixed, prepares ball milling
Mixing is then placed in ball mill progress ball milling 10min, then the solid material after gained ball milling is put into mold carry out at
Type；
(3) the mold 8h disposed within that will be put into the solid material after the step (2) ball milling is stood, during which at interval of
Solid material surface of the 2h into mold sprays a small amount of water, to keep solid material wet；
(4) by the step (3) mold and solid material be put into tube furnace together, water is passed through into tube furnace
Steam, control vapor flow are 0.2ml/min, start tube furnace temperature programming system, in 200 DEG C of progress 22h constant temperature processing；
(5) after to the constant temperature processing routine of the step (4), continue to be passed through vapor into tube furnace, and control
Vapor flow is 0.1ml/min, and the time that control is passed through vapor is 2h, is post-processed；
(6) after the post-processing of the step (4), mold and solid material is taken out from tube furnace, makes mould at room temperature
Tool and solid material are dried, and after to be dried, are demoulded to solid material to get integral catalyzer is arrived.
As shown in Figure 1, being molded under 200 DEG C of cryogenic conditions for monolithic catalyst manufactured in the present embodiment can be completed, material
Connection possesses good mechanical strength based on ionic bond and covalent bond, supplemented by hydrogen bond and Van der Waals force between substance in material.This
The monolithic catalyst after molding for implementing preparation is tested through experiment, axial compression strength 260N/cm2, radial pressure resistance
Spend 90N/cm2, wear strength 0.84%/kg, the fine cracks quantity of unilateral end face is at 3-7, and crack width
≤ 0.031mm, crack length are the 29% of catalyst total length.Compared to the use of general preformed catalyst, this implementation is used
Not only surface possesses good catalytic effect to the integral catalyzer of example method preparation, but also when the active component on surface falls off
Afterwards, also there is good catalytic activity after internal component is exposed, this not only adds the service lifes of catalyst, and
Compared to conventional catalyst, the use of the catalyst reduces catalyst change expense.
Embodiment two
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a method of integral catalyzer is prepared using waste sill, with manganese mud, flyash
It is the raw material for preparing integral catalyzer with plasma glass slag, its step are as follows:
Step 1: waste sill is activated, steps are as follows for specific activation method:
A. this step is the same as example 1；
B. the manganese mud waste original washing powder material for taking 1g to prepare in the step a is added 25ml and prepares in the step a
HNO3Solution is mixed, and after stirring 30min, is added a certain amount of prepared NaOH solution in the step a, is made
Solution is controlled in pH 8.5~9, and after being stirred for 30min, centrifuging and taking solid is spare；
C. the solid obtained in the step b is put into progress 5h drying process in 100 DEG C of baking oven, it is dry to solid
Afterwards, solid transfer is placed in Muffle furnace, then starts Muffle furnace temperature programming system, 3h is carried out under 400 DEG C of constant temperature
High-temperature process then takes out solid material, spare；
Step 2: being mixed with chemically bonded ceramics catalyst using waste base, monoblock type catalysis is obtained by moulding process
Agent, method and step are as follows:
(1) this step is the same as example 1；
(2) 3g flyash, 2.5g plasma glass slag and the 2.39g activated processing in the step 1 are in addition taken
The solid material of preparation is mixed, and mixed raw material is obtained, and then according to measuring based on mixed raw material total amount, is added relative to mixed
The CaO that the mass ratio of raw material is 5% is closed, the preparation in the step (1) for being 3% relative to the mass ratio of mixed raw material is added
Auxiliary exciting agent, and be added relative to mixed raw material mass ratio be 35% H2O, is carried out uniformly mixed, prepares ball milling
Mixing is then placed in ball mill progress ball milling 10min, then the solid material after gained ball milling is put into mold carry out at
Type；
(3) this step is the same as example 1；
(4) this step is the same as example 1；
(5) after to the constant temperature processing routine of the step (4), continue to be passed through vapor into tube furnace, and control
Vapor flow is 0.1ml/min, and the time that control is passed through vapor is 3h, is post-processed；
(6) this step is the same as example 1.
Being molded under 200 DEG C of cryogenic conditions for monolithic catalyst manufactured in the present embodiment can be completed, in material substance it
Between connection based on ionic bond and covalent bond, supplemented by hydrogen bond and Van der Waals force, possess good mechanical strength.This implementation preparation
Monolithic catalyst after molding is tested through experiment, axial compression strength 252N/cm2, radial crushing strength 88N/cm2,
Wear strength is 0.92%/kg, and the fine cracks quantity of unilateral end face is at 3-7, and crackle Kuan Du≤0.034mm, is split
Line length is the 30% of catalyst total length.Compared to the use of general preformed catalyst, prepared using the present embodiment method
Not only surface possesses good catalytic effect to integral catalyzer, but also after the active component when surface falls off, internal component
Also there is good catalytic activity, this not only adds the service lifes of catalyst, and urge compared to conventional after being exposed
Agent, the use of the catalyst reduce catalyst change expense.
Embodiment three
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a method of preparing integral catalyzer using waste sill, be with waste sill
The raw material of integral catalyzer are prepared, its step are as follows:
Step 1: waste sill is activated, steps are as follows for specific activation method:
A. this step is the same as example 1；
B. the blast-furnace cinder waste original washing powder material for taking 3g to prepare in the step a, the blast furnace for being used in activation process
Slag waste sill constituent mass content are as follows: the content of transition metal is 10%, SiO2For 35%, Al2O3For 12%, K2O is
0.8%, MgO 0.5%；25ml prepared HNO in the step a is added3Solution is mixed, after stirring 30min, then
A certain amount of prepared NaOH solution in the step a is added, controls solution 8~8.5 in pH, is stirred for 30min
Afterwards, centrifuging and taking solid, it is spare；
C. this step is the same as example 1；
Step 2: being mixed with chemically bonded ceramics catalyst using waste base, monoblock type catalysis is obtained by moulding process
Agent, method and step are as follows:
(1) this step is the same as example 1；
(2) 2.5g flyash and 3g phosphorus slag waste sill and the 2.39g activated processing system in the step 1 are in addition taken
Standby solid material is mixed, and mixed raw material is obtained, the other waste sill group sub-prime for using in forming process
Measure content are as follows: SiO2For 28%, Al2O3For 15%, CaO 40%, SO3It is 1.5%；It then is base according to mixed raw material total amount
Plinth amount, be added relative to mixed raw material mass ratio be 5% CaO, be added relative to mixed raw material mass ratio be 3%
The auxiliary exciting agent prepared in the step (1), and the H for being 35% relative to the mass ratio of mixed raw material is added2O is carried out
It is uniformly mixed, prepares ball mill mixing, be then placed in ball mill progress ball milling 10min, then by the solid material after gained ball milling
It is put into mold and is formed；
(3) this step is the same as example 1；
(4) this step is the same as example 1；
(5) this step is the same as example 1；
(6) this step is the same as example 1.
As shown in Figure 1, being molded under 200 DEG C of cryogenic conditions for monolithic catalyst manufactured in the present embodiment can be completed, material
Connection possesses good mechanical strength based on ionic bond and covalent bond, supplemented by hydrogen bond and Van der Waals force between substance in material.This
The monolithic catalyst after molding for implementing preparation is tested through experiment, axial compression strength 270N/cm2, radial pressure resistance
Spend 94N/cm2, wear strength 0.82%/kg, the fine cracks quantity of unilateral end face is at 3-7, and crack width
≤ 0.025mm, crack length are the 26% of catalyst total length.Compared to the use of general preformed catalyst, this implementation is used
Not only surface possesses good catalytic effect to the integral catalyzer of example method preparation, but also when the active component on surface falls off
Afterwards, also there is good catalytic activity after internal component is exposed, this not only adds the service lifes of catalyst, and
Compared to conventional catalyst, the use of the catalyst reduces catalyst change expense.
Example IV
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a method of preparing integral catalyzer using waste sill, be with waste sill
The raw material of integral catalyzer are prepared, its step are as follows:
Step 1: waste sill is activated, steps are as follows for specific activation method:
A. this step is the same as example 1；
B. the iron tailings waste original washing powder material for taking 3g to prepare in the step a, the iron tailings for being used in activation process
Waste sill constituent mass content are as follows: the content of transition metal is 8%, SiO2For 30%, Al2O3For 12%, K2O is
1.3%, MgO 0.8%；25ml prepared HNO in the step a is added3Solution is mixed, after stirring 30min, then
A certain amount of prepared NaOH solution in the step a is added, controls solution 8~8.5 in pH, is stirred for 30min
Afterwards, centrifuging and taking solid, it is spare；
C. this step is the same as example 1；
Step 2: being mixed with chemically bonded ceramics catalyst using waste base, monoblock type catalysis is obtained by moulding process
Agent, method and step are as follows:
(1) this step is the same as example 1；
(2) 3.5g phosphorus slag and 2g flyash waste sill and the 2.39g activated processing in the step 1 is in addition taken to make
Standby solid material is mixed, and mixed raw material is obtained, the other waste sill group sub-prime for using in forming process
Measure content are as follows: SiO2For 25%, Al2O3For 9%, CaO 38%, SO3It is 2%；Then according to mixed raw material total amount based on
Amount, be added relative to mixed raw material mass ratio be 5% CaO, be added relative to mixed raw material mass ratio for 3% in institute
The auxiliary exciting agent prepared in step (1) is stated, and the H for being 35% relative to the mass ratio of mixed raw material is added2O is mixed
It closes uniformly, prepares ball mill mixing, be then placed in progress ball milling 10min in ball mill, then the solid material after gained ball milling is put
Enter in mold and is formed；
(3) this step is the same as example 1；
(4) this step is the same as example 1；
(5) this step is the same as example 1；
(6) this step is the same as example 1.
As shown in Figure 1, being molded under 200 DEG C of cryogenic conditions for monolithic catalyst manufactured in the present embodiment can be completed, material
Connection possesses good mechanical strength based on ionic bond and covalent bond, supplemented by hydrogen bond and Van der Waals force between substance in material.This
The monolithic catalyst after molding for implementing preparation is tested through experiment, axial compression strength 280N/cm2, radial pressure resistance
Spend 100N/cm2, wear strength 0.80%/kg, the fine cracks quantity of unilateral end face is at 3-7, and crack width
≤ 0.010mm, crack length are the 25% of catalyst total length.Compared to the use of general preformed catalyst, this implementation is used
Not only surface possesses good catalytic effect to the integral catalyzer of example method preparation, but also when the active component on surface falls off
Afterwards, also there is good catalytic activity after internal component is exposed, this not only adds the service lifes of catalyst, and
Compared to conventional catalyst, the use of the catalyst reduces catalyst change expense.
Embodiment five
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a method of preparing integral catalyzer using waste sill, be with waste sill
The raw material of integral catalyzer are prepared, its step are as follows:
Step 1: waste sill is activated, steps are as follows for specific activation method:
A. this step is the same as example 1；
B. the manganese mud waste original washing powder material for taking 3g to prepare in the step a, the manganese mud for being used in activation process
Waste sill constituent mass content are as follows: the content of transition metal is 15%, SiO2For 42%, Al2O3For 20%, K2O is
1.3%, MgO 0.8%；25ml prepared HNO in the step a is added3Solution is mixed, after stirring 30min, then
A certain amount of prepared NaOH solution in the step a is added, controls solution 8~8.5 in pH, is stirred for 30min
Afterwards, centrifuging and taking solid, it is spare；
C. this step is the same as example 1；
Step 2: being mixed with chemically bonded ceramics catalyst using waste base, monoblock type catalysis is obtained by moulding process
Agent, method and step are as follows:
(1) this step is the same as example 1；
(2) in addition take 1.5g flyash, 2g plasma slag and 2g phosphorus slag waste sill and 2.39g in the step
The solid material of activated processing preparation is mixed in 1, obtains mixed raw material, other useless for what is used in forming process
Object sill constituent mass content are as follows: SiO2For 33%, Al2O3For 17%, CaO 48%, SO3It is 2%；Then according to mixing
It is measured based on raw material total amount, the CaO for being 5% relative to the mass ratio of mixed raw material is added, the matter relative to mixed raw material is added
It measures than the auxiliary exciting agent prepared in the step (1) for 3%, and being added relative to the mass ratio of mixed raw material is 35%
H2O, is carried out uniformly mixed, prepares ball mill mixing, is then placed in progress ball milling 10min in ball mill, then by gained ball milling
Solid material afterwards, which is put into mold, to be formed；
(3) this step is the same as example 1；
(4) this step is the same as example 1；
(5) this step is the same as example 1；
(6) this step is the same as example 1.
As shown in Figure 1, being molded under 200 DEG C of cryogenic conditions for monolithic catalyst manufactured in the present embodiment can be completed, material
Connection possesses good mechanical strength based on ionic bond and covalent bond, supplemented by hydrogen bond and Van der Waals force between substance in material.This
The monolithic catalyst after molding for implementing preparation is tested through experiment, axial compression strength 265N/cm2, radial pressure resistance
Spend 90N/cm2, wear strength 0.86%/kg, the fine cracks quantity of unilateral end face is at 3-7, and crack width
≤ 0.027mm, crack length are the 30% of catalyst total length.Compared to the use of general preformed catalyst, this implementation is used
Not only surface possesses good catalytic effect to the integral catalyzer of example method preparation, but also when the active component on surface falls off
Afterwards, also there is good catalytic activity after internal component is exposed, this not only adds the service lifes of catalyst, and
Compared to conventional catalyst, the use of the catalyst reduces catalyst change expense.
Based on the above embodiments it is found that above-described embodiment with waste base is the raw material for preparing integral catalyzer, use
A variety of waste bases prepare catalyst efficient cryogenic integral catalyzer, are broadly divided into activation and molding two during the preparation process
Point.Compared to traditional preparation method, above-described embodiment method is being no more than 200 DEG C of moldings that catalyst can be completed, molding
Connection has good machinery based on ionic bond and covalent bond, supplemented by hydrogen bond and Van der Waals force between substance in rear catalyst
Intensity.Not only surface possesses good catalytic effect to the catalyst, but also after the active component when surface falls off, internal component
Also there is good catalytic activity, this not only adds the service lifes of catalyst, and urge compared to conventional after being exposed
Agent, the use of the catalyst reduce catalyst change expense.The preparation method of the catalyst has novel, simple, efficient
The characteristics of.The above embodiment of the present invention solves current problems transition-metal catalyst production and used, and reduces catalyst
Use cost, the above embodiment of the present invention provides a kind of method for preparing integral catalyzer using a variety of waste bases, makes
The production and application cost for obtaining catalyst is effectively reduced and can be effectively applied in industry.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
The technical principle and inventive concept for being prepared the method for integral catalyzer using waste sill without departing from the present invention, are all belonged to
In protection scope of the present invention.
Claims (8)
1. a kind of method for preparing integral catalyzer using waste sill, which is characterized in that the waste sill, which has, to be contained
There are transition metal slag, clinker or slag, its step are as follows:
Step 1: waste sill is activated, steps are as follows for specific activation method:
A. compound concentration is the HNO of 1mol/L3The NaOH solution that solution and concentration are 1mol/L, it is spare；And waste sill is taken,
By crushed 50 meshes, waste original washing powder material is obtained, it is spare；
B. a certain amount of waste original washing powder material prepared in the step a is taken, addition is a certain amount of to be prepared in the step a
HNO3Solution is mixed, waste original washing powder material and HNO3The ratio of solution mixing is (1~3) g:25mL, stirs at least 30min
Afterwards, add a certain amount of prepared NaOH solution in the step a, make solution pH control 8~9, be stirred for
After few 30min, centrifuging and taking solid is spare；
C. the solid obtained in the step b is put into progress 5-8h drying process in the baking oven not higher than 100 DEG C, to solid
After drying, solid transfer is placed in Muffle furnace, Muffle furnace temperature programming system is then started, is being not higher than 400 DEG C of perseverance
Temperature is lower to carry out at least 3h high-temperature process, then takes out solid material, spare；
Step 2: it is mixed with chemically bonded ceramics catalyst using waste base, integral catalyzer is obtained by moulding process,
Its method and step is as follows:
(1) auxiliary exciting agent is prepared, according to mass ratio K2O:Al2O3:SO3:H2O=1:1.2:0.3:1.5 mixes each drug
It closes, and stirs evenly, obtain auxiliary exciting agent, it is spare；
(2) a certain amount of waste sill and the solid material of processing preparation activated in the step 1 is in addition taken to be mixed
It closes, control mixing quality ratio is (2.3-3.1): 1, mixed raw material is obtained, then according to being measured based on mixed raw material total amount, is added
Enter the CaO for being 5% relative to the mass ratio of mixed raw material, being added relative to the mass ratio of mixed raw material is 3% in the step
Suddenly the auxiliary exciting agent prepared in (1), and the H for being 35% relative to the mass ratio of mixed raw material is added2O mix
It is even, ball mill mixing is prepared, is then placed in progress ball milling at least 10min in ball mill, then the solid material after gained ball milling is put
Enter in mold and is formed；
(3) the mold at least 8h disposed within that will be put into the solid material after the step (2) ball milling is stood, during which at interval of
Solid material surface of most 2h into mold sprays a small amount of water, to keep solid material wet；
(4) by the step (3) mold and solid material be put into tube furnace together, be passed through into tube furnace water steaming
Gas, control vapor flow are not higher than 0.2ml/min, start tube furnace temperature programming system, are carrying out at least not higher than 200 DEG C
The processing of 22h constant temperature；
(5) after to the constant temperature processing routine of the step (4), continue to be passed through vapor into tube furnace, and control flow
Not higher than 0.1ml/min, the time that control is passed through vapor is 2-3h, is post-processed；
(6) after the post-processing of the step (4), mold and solid material are taken out from tube furnace, make at room temperature mold and
Solid material is dried, and after to be dried, is demoulded to solid material to get integral catalyzer is arrived.
2. the method for preparing integral catalyzer using waste sill according to claim 1, which is characterized in that described
Waste sill constituent mass content in step 1, for being used in activation process are as follows: levels of transition metals 8-15%,
SiO2For 30-42%, Al2O3For 12-20%, K2O≤1.3%, MgO≤0.8%.
3. the method for preparing integral catalyzer using waste sill according to claim 2, which is characterized in that described
Waste sill constituent mass content in step 1, for being used in activation process are as follows: the content of transition metal is 10%,
SiO2For 35%, Al2O3For 12%, K2O is 0.8%, MgO 0.5%.
4. the method for preparing integral catalyzer using waste sill according to claim 1, which is characterized in that described
Other waste sill constituent mass content in step 2, for being used in forming process are as follows: SiO2For 25-33%, Al2O3
For 9-17%, CaO 38-48%, SO3≤ 2%.
5. the method for preparing integral catalyzer using waste sill according to claim 4, which is characterized in that described
Other waste sill constituent mass content in step 2, for being used in forming process are as follows: SiO2For 28%, Al2O3For
15%, CaO 40%, SO3It is 1.5%.
6. the method for preparing integral catalyzer using waste sill according to claim 1, which is characterized in that described
In step 2, the axial compression strength of prepared integral catalyzer is 220-280N/cm2, radial crushing strength 80-
100N/cm2, wear strength 0.080-0.10%/kg；The fine cracks of the unilateral end face of the integral catalyzer of preparation
Quantity is that 3-7 locates, and its crackle Kuan Du≤0.040mm, crack length for catalyst total length 25-33%.
7. the method for preparing integral catalyzer using waste sill according to claim 1, which is characterized in that described
In step 2, prepared integral catalyzer surface forms catalyst activity layer, when integral catalyzer table in use
After the active component in face falls off, the component inside integral catalyzer can be exposed, and form mesoporous type catalytic activity interface.
8. the method for preparing integral catalyzer using waste sill according to claim 1, which is characterized in that described
In step 2, connection is based on ionic bond and covalent bond between substance in prepared integral catalyzer material, hydrogen bond and Fan De
Supplemented by Hua Li.
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