CN109621944B - Method for preparing monolithic catalysts using waste-based materials - Google Patents
Method for preparing monolithic catalysts using waste-based materials Download PDFInfo
- Publication number
- CN109621944B CN109621944B CN201811429647.0A CN201811429647A CN109621944B CN 109621944 B CN109621944 B CN 109621944B CN 201811429647 A CN201811429647 A CN 201811429647A CN 109621944 B CN109621944 B CN 109621944B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- waste
- prepared
- solid
- monolithic catalyst
- 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.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention provides a method for preparing an integral catalyst by using waste base materials, which takes the waste base materials as raw materials for preparing the integral catalyst, mainly comprises two parts of activation and molding in the preparation process, the molding of the catalyst can be completed at the temperature of not more than 200 ℃, substances in the molded catalyst are mainly connected by ionic bonds and covalent bonds, and hydrogen bonds and van der Waals forces are assisted, so that the catalyst has good mechanical strength. The catalyst not only has good catalytic effect on the surface, but also has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the catalyst has the advantage that the catalyst replacement cost is reduced due to the use of the catalyst. The preparation method of the monolithic catalyst is novel, simple and efficient, has low cost, long service life, high strength, good activity and high quality, can realize waste recycling, is environment-friendly and has remarkable popularization value.
Description
Technical Field
The invention relates to a preparation method of an integral catalyst, and also relates to a waste recycling method, which is applied to the technical field of catalyst preparation and application.
Background
The catalyst is a substance which can change the chemical reaction rate of a reactant without changing the chemical balance in a chemical reaction, can improve or reduce the chemical reaction rate of the reactant, and has unchanged mass and chemical properties before and after the chemical reaction. According to statistics, about more than 90% of industrial processes use catalysts, such as chemical industry, petrochemical industry, biochemical industry, environmental protection and the like. The catalyst occupies an extremely important position in the modern chemical industry, the activity, selectivity and stability of the catalyst are important indexes for measuring the performance of the catalyst, and the noble metal catalyst and the transition metal catalyst are paid more attention with excellent activity, selectivity and stability and are widely applied to various fields. Among them, the transition metal catalyst has high catalytic activity, good durability and low cost, and is gradually becoming a key point in the field of catalysts. However, the cost aspect of the use of catalysts in industrial processes is still high. In order to change the current situation, the preparation of the catalyst by using the slag, the slag or the tailings containing the transition metal is applied to the industry, so that the added value of waste base can be improved, and the production and use cost of the catalyst can be reduced. However, the process is not mature enough to produce secondary pollution during the production process or to fully utilize waste base.
At present, most and mature catalysts are powder catalysts, and the powder catalysts have the defects of large pressure drop, easiness in purging, low mechanical strength and the like, and particularly, for flue gas containing fly ash, catalyst bed layer blockage is easily caused, so that in actual industrial application, the monolithic catalysts are adopted and have irreplaceable advantages, such as:
1. the pressure drop of the bed layer is obviously lower;
2. the mass transfer efficiency is obviously improved;
3. the amplification effect is less pronounced;
4. the separation and regeneration of the monolithic catalyst is relatively easy.
The monolithic catalysts used in the market mainly include plate type, honeycomb type and corrugated plate type catalysts, all of which have good activity, but still face many problems in the catalyst forming process, such as:
1. when the integral catalyst is prepared by using an impregnation method, the active components are easy to fall off and the loading rate is not high;
2. when the blending extrusion molding method is used for preparing the monolithic catalyst, the consumption of the catalyst core component is large, and the economy is poor;
3. during the catalyst forming process, calcination at high temperature above 1100 ℃ is required to improve the mechanical properties of the catalyst, which leads to deactivation of active components in the catalyst and reduces the performance of the catalyst.
Therefore, a new technical means is urgently needed to be found to solve the problems of production and use of the current transition metal catalyst, including the problem of overhigh production and use cost of the catalyst, the problem of secondary pollution caused by waste-based preparation of the catalyst, and the problem of whether various indexes of catalyst molding can meet industrial requirements.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a method for preparing a monolithic catalyst by using waste base materials, the catalyst can be molded at the temperature of not more than 200 ℃, substances in the molded monolithic catalyst are mainly connected by ionic bonds and covalent bonds, and have good mechanical strength by taking hydrogen bonds and van der waals force as assistance. The catalyst not only has good catalytic effect on the surface, but also has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the catalyst has the advantage that the catalyst replacement cost is reduced due to the use of the catalyst. The preparation method of the monolithic catalyst is novel, simple and efficient, has low cost, long service life of the catalyst, high strength, good activity and high quality, can realize waste recycling, is environment-friendly, saves energy and reduces carbon, has great significance for controlling environmental pollution, and has obvious popularization value.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of making a monolithic catalyst using a waste based material having a slag, slag or ash containing transition metals, comprising the steps of:
step 1: the waste base material is subjected to activation treatment, and the specific activation method comprises the following steps:
a. preparing HNO with the concentration of 1mol/L3The solution and NaOH solution with the concentration of 1mol/L are reserved; taking waste base materials, crushing and sieving by a 50-mesh sieve to obtain waste base powder for later use;
b. taking a certain amount of waste-based powder prepared in the step a, adding a certain amount of HNO prepared in the step a3Mixing the solution, waste-based powder and HNO3The mixing ratio of the solution is (1-3) g: 25mL, stirring for at least 30min, adding a certain amount of NaOH solution prepared in the step a to control the pH of the solution to be 8-9, stirring for at least 30min, and centrifuging to obtain a solid for later use;
c. putting the solid obtained in the step b into an oven with the temperature not higher than 100 ℃ for drying treatment for 5-8h, transferring the solid into a muffle furnace after the solid is dried, starting a muffle furnace temperature programming system, carrying out high-temperature treatment for at least 3h at the constant temperature not higher than 400 ℃, and taking out the solid material for later use;
step 2: the method comprises the following steps of preparing a chemically bonded ceramic catalyst by waste base mixing, and obtaining an integral catalyst by a forming process:
(1) preparing an auxiliary activator according to K2O:Al2O3:SO3:H2Mixing the medicines according to the mass ratio of 1:1.2:0.3:1.5, and uniformly stirring to obtain an auxiliary exciting agent for later use;
(2) mixing a certain amount of waste base material with the solid material prepared by the activation treatment in the step 1, controlling the mixing mass ratio to be (2.3-3.1):1 to obtain a mixed raw material, then adding 5% of CaO in mass ratio relative to the mixed raw material, 3% of auxiliary excitant prepared in the step (1) in mass ratio relative to the mixed raw material and 35% of H in mass ratio relative to the mixed raw material according to the total amount of the mixed raw material as a basic amount2O, mixing the materials evenly to prepare a ball milling mixed material, and then putting the mixed material into a ball millPerforming ball milling for at least 10min, and then placing the obtained ball-milled solid material into a mould for molding;
(3) placing the mould into which the solid material subjected to ball milling in the step (2) is placed in a chamber for standing for at least 8 hours, and spraying a small amount of water to the surface of the solid material in the mould at intervals of at most 2 hours to keep the solid material moist;
(4) putting the mould and the solid material in the step (3) into a tubular furnace, introducing steam into the tubular furnace, controlling the flow rate of the steam to be not higher than 0.2ml/min, starting a tubular furnace temperature programming system, and carrying out constant temperature treatment for at least 22h at the temperature of not higher than 200 ℃;
(5) after the constant temperature treatment procedure in the step (4) is finished, continuously introducing water vapor into the tubular furnace, controlling the flow rate to be not higher than 0.1ml/min, controlling the time of introducing the water vapor to be 2-3h, and performing post-treatment;
(6) and (4) after the post-treatment in the step (4) is finished, taking out the mold and the solid material from the tube furnace, drying the mold and the solid material at room temperature, and demolding the solid material after drying to obtain the monolithic catalyst.
As a preferred technical solution of the present invention, in the step 1, the waste-based material used in the activation process comprises the following components by mass: the content of transition metal is 8-15%, SiO230-42% of Al2O312-20% of K2O is less than or equal to 1.3 percent, and MgO is less than or equal to 0.8 percent. The optimal components for the waste based material used in the activation process are by mass: the content of transition metal is 10%, SiO235% of Al2O312% of K20.8% of O and 0.5% of MgO.
As a preferred technical solution of the present invention, in the step 2, the additional waste-based material used in the forming process comprises the following components by mass: SiO 2225-33% of Al2O39-17 percent of CaO, 38-48 percent of CaO and SO3≦ 2%. The optimum component mass content of the additional waste based material used in the forming process is: SiO 2228% of Al2O315 percent of CaO, 40 percent of CaO and SO3The content was 1.5%.
As a preferred technical proposal of the invention, in the step 2, the axial compressive strength of the prepared monolithic catalyst is 220-280N/cm2The radial compressive strength of the material is 80-100N/cm2The abrasion resistance is 0.080-0.10%/kg; the number of fine cracks on the single-side end face of the prepared monolithic catalyst is 3-7, the crack width is less than or equal to 0.040mm, and the crack length is 25-33% of the total length of the catalyst.
As a preferred technical scheme of the present invention, in the step 2, a catalyst active layer is formed on the surface of the prepared monolithic catalyst, and when the active components on the surface of the monolithic catalyst fall off during the use of the monolithic catalyst, the components inside the monolithic catalyst can be exposed to form a mesoporous catalytic active interface.
As a preferred technical solution of the present invention, in the step 2, the substance in the prepared monolithic catalyst material is mainly connected by ionic bonds and covalent bonds, and is assisted by hydrogen bonds and van der waals forces.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. compared with the traditional preparation of the formed catalyst, the method has the advantages that the catalyst is prepared by using waste base, the waste base is mainly derived from slag, furnace slag and the like and is mainly divided into two steps of activation and forming, so that the preparation of the catalyst can be finished, and the method is simple, easy to realize, low in preparation cost and easy to control;
2. compared with the common catalyst forming and calcining temperature of 1100 ℃ or above, the method of the invention can complete the forming of the prepared catalyst at the low temperature of 200 ℃, and the connection among substances in the material is mainly ionic bonds and covalent bonds, and is assisted by hydrogen bonds and Van der Waals force, thus having good mechanical strength.
3. Compared with the use of common molded catalysts, the monolithic catalyst prepared by the method has good catalytic effect on the surface, and has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the use of the catalyst reduces the replacement cost of the catalyst.
Drawings
FIG. 1 is a process flow diagram of a method of making a monolithic catalyst using waste based materials in accordance with an embodiment of the present invention.
Detailed Description
The following description is given in conjunction with specific examples, which describe preferred embodiments of the invention in detail as follows:
example one
In this example, referring to fig. 1, a method for preparing a monolithic catalyst from waste-based materials, using manganese slag, fly ash and plasma glass slag as raw materials for preparing the monolithic catalyst, comprises the following steps:
step 1: the waste base material is subjected to activation treatment, and the specific activation method comprises the following steps:
a. preparing HNO with the concentration of 1mol/L3The solution and NaOH solution with the concentration of 1mol/L are reserved; crushing the manganese slag, and sieving the crushed manganese slag with a 50-mesh sieve to obtain manganese slag waste-based powder for later use;
b. taking 3g of manganese slag waste-based powder prepared in the step a, and adding 25ml of HNO prepared in the step a3Mixing the solutions, stirring for 30min, adding a certain amount of NaOH solution prepared in the step a to control the pH of the solution to be 8-8.5, stirring for 30min, and centrifuging to obtain a solid for later use;
c. putting the solid obtained in the step b into a drying oven at 100 ℃ for drying treatment for 8h, transferring the solid into a muffle furnace after the solid is dried, starting a muffle furnace temperature programming system, carrying out high-temperature treatment for 3h at the constant temperature of 400 ℃, and taking out the solid material for later use;
step 2: the method comprises the following steps of preparing a chemically bonded ceramic catalyst by waste base mixing, and obtaining an integral catalyst by a forming process:
(1) preparing an auxiliary excitant according to the mass ratio K2O:Al2O3:SO3:H2Mixing the medicines at a ratio of 1:1.2:0.3:1.5, and uniformly stirring to obtain an auxiliary exciting agent for later use;
(2) mixing 3g of fly ash, 2.5g of plasma glass slag and 1.77g of solid material prepared by activation treatment in the step 1 to obtain a mixed raw material, adding 5% of CaO in mass ratio relative to the mixed raw material, 3% of auxiliary excitant prepared in the step (1) in mass ratio relative to the mixed raw material and 35% of H in mass ratio relative to the mixed raw material according to the total amount of the mixed raw material as a basic amount, and adding2O, uniformly mixing the materials to prepare a ball-milling mixed material, then putting the ball-milling mixed material into a ball mill to perform ball milling for 10min, and putting the obtained ball-milled solid material into a mould to perform moulding;
(3) placing the mould into which the solid material subjected to ball milling in the step (2) is placed in a chamber for 8 hours and standing, and spraying a small amount of water to the surface of the solid material in the mould every 2 hours to keep the solid material moist;
(4) putting the mould and the solid material in the step (3) into a tubular furnace, introducing steam into the tubular furnace, controlling the flow of the steam to be 0.2ml/min, starting a tubular furnace temperature programming system, and carrying out constant temperature treatment for 22h at 200 ℃;
(5) after the constant temperature treatment procedure in the step (4) is finished, continuously introducing steam into the tubular furnace, controlling the flow rate of the steam to be 0.1ml/min and the time for introducing the steam to be 2 hours, and performing post-treatment;
(6) and (4) after the post-treatment in the step (4) is finished, taking out the mold and the solid material from the tube furnace, drying the mold and the solid material at room temperature, and demolding the solid material after drying to obtain the monolithic catalyst.
As shown in fig. 1, the monolithic catalyst prepared in this example can be molded at a low temperature of 200 ℃, and the materials have good mechanical strength, mainly including ionic bonds and covalent bonds, and assisted by hydrogen bonds and van der waals forces. The axial compression strength of the formed monolithic catalyst prepared by the implementation is 260N/cm through experimental tests2Radial compressive strength of 90N/cm2The abrasion resistance is 0.84%/kg, the number of fine cracks on one side end face is 3-7, the crack width is less than or equal to 0.031mm, and the crack length is 29% of the total length of the catalyst. Compared with the use of a common molded catalyst, the monolithic catalyst prepared by the method not only has good catalytic effect on the surface, but also has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the use of the catalyst reduces the replacement cost of the catalyst.
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for preparing a monolithic catalyst from waste-based materials, using manganese slag, fly ash and plasma glass slag as raw materials for preparing the monolithic catalyst, includes the following steps:
step 1: the waste base material is subjected to activation treatment, and the specific activation method comprises the following steps:
a. the step is the same as the first embodiment;
b. taking 1g of manganese slag waste-based powder prepared in the step a, and adding 25ml of HNO prepared in the step a3Mixing the solutions, stirring for 30min, adding a certain amount of NaOH solution prepared in the step a to control the pH of the solution to be 8.5-9, stirring for 30min, and centrifuging to obtain a solid for later use;
c. putting the solid obtained in the step b into a drying oven at 100 ℃ for drying treatment for 5h, transferring the solid into a muffle furnace after the solid is dried, starting a muffle furnace temperature programming system, carrying out high-temperature treatment for 3h at the constant temperature of 400 ℃, and taking out the solid material for later use;
step 2: the method comprises the following steps of preparing a chemically bonded ceramic catalyst by waste base mixing, and obtaining an integral catalyst by a forming process:
(1) the step is the same as the first embodiment;
(2) taking 3g of pulverized coalMixing ash, 2.5g of plasma glass slag and 2.39g of the solid material prepared by the activation treatment in the step 1 to obtain a mixed raw material, then adding 5% by mass of CaO relative to the mixed raw material, 3% by mass of the auxiliary activator prepared in the step (1) relative to the mixed raw material, and 35% by mass of H relative to the mixed raw material, based on the total amount of the mixed raw material2O, uniformly mixing the materials to prepare a ball-milling mixed material, then putting the ball-milling mixed material into a ball mill to perform ball milling for 10min, and putting the obtained ball-milled solid material into a mould to perform moulding;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) after the constant temperature treatment procedure in the step (4) is finished, continuously introducing steam into the tubular furnace, controlling the flow rate of the steam to be 0.1ml/min and the time for introducing the steam to be 3 hours, and performing post-treatment;
(6) the procedure is the same as in the first embodiment.
The monolithic catalyst prepared by the embodiment can be molded at a low temperature of 200 ℃, and substances in the material are mainly connected by ionic bonds and covalent bonds, and have good mechanical strength by taking hydrogen bonds and van der waals force as assistance. The axial compression strength of the formed monolithic catalyst prepared by the implementation is 252N/cm through experimental tests2Radial compressive strength of 88N/cm2The abrasion resistance is 0.92%/kg, the number of fine cracks on one side end face is 3-7, the crack width is less than or equal to 0.034mm, and the crack length is 30% of the total length of the catalyst. Compared with the use of a common molded catalyst, the monolithic catalyst prepared by the method not only has good catalytic effect on the surface, but also has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the use of the catalyst reduces the replacement cost of the catalyst.
EXAMPLE III
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a method for preparing a monolithic catalyst from waste-based materials, which uses waste-based materials as raw materials for preparing the monolithic catalyst, comprises the following steps:
step 1: the waste base material is subjected to activation treatment, and the specific activation method comprises the following steps:
a. the step is the same as the first embodiment;
b. taking 3g of the blast furnace slag waste base powder prepared in the step a, wherein the blast furnace slag waste base material used in the activation process comprises the following components in percentage by mass: the content of transition metal is 10%, SiO235% of Al2O312% of K20.8 percent of O and 0.5 percent of MgO; adding 25ml of HNO prepared in the step a3Mixing the solutions, stirring for 30min, adding a certain amount of NaOH solution prepared in the step a to control the pH of the solution to be 8-8.5, stirring for 30min, and centrifuging to obtain a solid for later use;
c. the step is the same as the first embodiment;
step 2: the method comprises the following steps of preparing a chemically bonded ceramic catalyst by waste base mixing, and obtaining an integral catalyst by a forming process:
(1) the step is the same as the first embodiment;
(2) and 2.5g of fly ash and 3g of phosphorus slag waste-based material are mixed with 2.39g of solid material prepared by activation treatment in the step 1 to obtain a mixed raw material, and the mixed raw material is used in the forming process and comprises the following other waste-based material components in percentage by mass: SiO 2228% of Al2O315 percent of CaO, 40 percent of CaO and SO31.5 percent; then adding 5% by mass of CaO relative to the total amount of the mixed raw materials, 3% by mass of the auxiliary activator prepared in the step (1) relative to the mixed raw materials, and 35% by mass of H relative to the mixed raw materials, based on the total amount of the mixed raw materials2O, uniformly mixing the materials to prepare a ball-milling mixed material, then putting the mixed material into a ball mill to perform ball milling for 10min, putting the obtained ball-milled solid material into a die, and feeding the solid material into the dieLine forming;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) the procedure is the same as in the first embodiment.
As shown in fig. 1, the monolithic catalyst prepared in this example can be molded at a low temperature of 200 ℃, and the materials have good mechanical strength, mainly including ionic bonds and covalent bonds, and assisted by hydrogen bonds and van der waals forces. The axial compression strength of the formed monolithic catalyst prepared by the implementation is 270N/cm through experimental tests2The radial compressive strength of the steel sheet is 94N/cm2The abrasion resistance is 0.82%/kg, the number of fine cracks on one side end face is 3-7, the crack width is less than or equal to 0.025mm, and the crack length is 26% of the total length of the catalyst. Compared with the use of a common molded catalyst, the monolithic catalyst prepared by the method not only has good catalytic effect on the surface, but also has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the use of the catalyst reduces the replacement cost of the catalyst.
Example four
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a method for preparing a monolithic catalyst from waste-based materials, which uses waste-based materials as raw materials for preparing the monolithic catalyst, comprises the following steps:
step 1: the waste base material is subjected to activation treatment, and the specific activation method comprises the following steps:
a. the step is the same as the first embodiment;
b. taking 3g of the iron tailing waste base powder prepared in the step a, wherein the iron tailing waste base material used in the activation process comprises the following components in percentage by mass: the content of transition metal is 8 percent, SiO230% of Al2O312% of K21.3 percent of O and 0.8 percent of MgO; adding 25ml of HNO prepared in the step a3Mixing the solutions, stirring for 30min, adding a certain amount of NaOH solution prepared in the step a to control the pH of the solution to be 8-8.5, stirring for 30min, and centrifuging to obtain a solid for later use;
c. the step is the same as the first embodiment;
step 2: the method comprises the following steps of preparing a chemically bonded ceramic catalyst by waste base mixing, and obtaining an integral catalyst by a forming process:
(1) the step is the same as the first embodiment;
(2) and additionally, mixing 3.5g of phosphorous slag, 2g of fly ash waste-based material and 2.39g of solid material prepared by activation treatment in the step 1 to obtain a mixed raw material, wherein the mixed raw material is used in the forming process and comprises the following additional waste-based material components in percentage by mass: SiO 2225% of Al2O39 percent of CaO, 38 percent of CaO and SO3Is 2%; then adding 5% by mass of CaO relative to the total amount of the mixed raw materials, 3% by mass of the auxiliary activator prepared in the step (1) relative to the mixed raw materials, and 35% by mass of H relative to the mixed raw materials, based on the total amount of the mixed raw materials2O, uniformly mixing the materials to prepare a ball-milling mixed material, then putting the ball-milling mixed material into a ball mill to perform ball milling for 10min, and putting the obtained ball-milled solid material into a mould to perform moulding;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) the procedure is the same as in the first embodiment.
As shown in fig. 1, the monolithic catalyst prepared in this example can be molded at a low temperature of 200 ℃, and the materials have good mechanical strength, mainly including ionic bonds and covalent bonds, and assisted by hydrogen bonds and van der waals forces. The axial compression strength of the formed monolithic catalyst prepared by the implementation is 280N/cm through experimental tests2Radial compressive strength thereof100N/cm2The abrasion resistance is 0.80%/kg, the number of fine cracks on one side end face is 3-7, the crack width is less than or equal to 0.010mm, and the crack length is 25% of the total length of the catalyst. Compared with the use of a common molded catalyst, the monolithic catalyst prepared by the method not only has good catalytic effect on the surface, but also has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the use of the catalyst reduces the replacement cost of the catalyst.
EXAMPLE five
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a method for preparing a monolithic catalyst from waste-based materials, which uses waste-based materials as raw materials for preparing the monolithic catalyst, comprises the following steps:
step 1: the waste base material is subjected to activation treatment, and the specific activation method comprises the following steps:
a. the step is the same as the first embodiment;
b. taking 3g of the manganese slag waste-based powder prepared in the step a, wherein the manganese slag waste-based powder used in the activation process comprises the following components in percentage by mass: the content of transition metal is 15 percent, SiO242% of Al2O320% of K21.3 percent of O and 0.8 percent of MgO; adding 25ml of HNO prepared in the step a3Mixing the solutions, stirring for 30min, adding a certain amount of NaOH solution prepared in the step a to control the pH of the solution to be 8-8.5, stirring for 30min, and centrifuging to obtain a solid for later use;
c. the step is the same as the first embodiment;
step 2: the method comprises the following steps of preparing a chemically bonded ceramic catalyst by waste base mixing, and obtaining an integral catalyst by a forming process:
(1) the step is the same as the first embodiment;
(2) in addition, 1.5g of fly ash, 2g of plasma slag and 2g of phosphorus slag waste are takenMixing the material base material with 2.39g of the solid material prepared by the activation treatment in the step 1 to obtain a mixed raw material, wherein the mixed raw material is used in the forming process and comprises the following additional waste material base material components in percentage by mass: SiO 2233% of Al2O317 percent of CaO, 48 percent of CaO and SO3Is 2%; then adding 5% by mass of CaO relative to the total amount of the mixed raw materials, 3% by mass of the auxiliary activator prepared in the step (1) relative to the mixed raw materials, and 35% by mass of H relative to the mixed raw materials, based on the total amount of the mixed raw materials2O, uniformly mixing the materials to prepare a ball-milling mixed material, then putting the ball-milling mixed material into a ball mill to perform ball milling for 10min, and putting the obtained ball-milled solid material into a mould to perform moulding;
(3) the step is the same as the first embodiment;
(4) the step is the same as the first embodiment;
(5) the step is the same as the first embodiment;
(6) the procedure is the same as in the first embodiment.
As shown in fig. 1, the monolithic catalyst prepared in this example can be molded at a low temperature of 200 ℃, and the materials have good mechanical strength, mainly including ionic bonds and covalent bonds, and assisted by hydrogen bonds and van der waals forces. The axial compression strength of the formed monolithic catalyst prepared by the implementation is 265N/cm through experimental tests2Radial compressive strength of 90N/cm2The abrasion resistance is 0.86%/kg, the number of fine cracks on one side end face is 3-7, the crack width is less than or equal to 0.027mm, and the crack length is 30% of the total length of the catalyst. Compared with the use of a common molded catalyst, the monolithic catalyst prepared by the method not only has good catalytic effect on the surface, but also has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the use of the catalyst reduces the replacement cost of the catalyst.
It can be seen from the above examples that the above examples use waste as raw materials for preparing monolithic catalysts, and use various waste to prepare low-temperature high-efficiency monolithic catalysts, and the preparation process is mainly divided into two parts, activation and molding. Compared with the traditional preparation method, the method of the embodiment can complete the molding of the catalyst at the temperature of not more than 200 ℃, and the molded catalyst has good mechanical strength because the connection among substances is mainly ionic bond and covalent bond and assisted by hydrogen bond and Van der Waals force. The catalyst not only has good catalytic effect on the surface, but also has good catalytic activity after the active components on the surface are removed and the internal components are exposed, so that the service life of the catalyst is prolonged, and compared with the conventional catalyst, the catalyst has the advantage that the catalyst replacement cost is reduced due to the use of the catalyst. The preparation method of the catalyst has the characteristics of novelty, simplicity and high efficiency. The above-described embodiments of the present invention solve many problems in the production and use of the current transition metal catalysts and reduce the use costs of the catalysts, and provide a method for preparing a monolith catalyst using various waste bases, so that the production and use costs of the catalysts are effectively reduced and can be effectively applied to the industry.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, but various changes may be made therein in accordance with the objects of the invention, and any changes, modifications, substitutions, combinations or simplifications made in accordance with the spirit and principles of the present invention shall be equivalently replaced as long as the objects of the present invention are met without departing from the technical principles and inventive concepts of the method for preparing monolithic catalysts from waste based materials.
Claims (4)
1. A method of making a monolithic catalyst using waste based materials, comprising the steps of:
step 1: the waste base material is subjected to activation treatment, and the specific activation method comprises the following steps:
a. the waste-based material comprises slag, slag or slag containing transition metal, and HNO with the concentration of 1mol/L is prepared3The solution and NaOH solution with the concentration of 1mol/L are reserved; taking waste base materials, crushing and sieving by a 50-mesh sieve to obtain waste base powder for later use; the waste base material comprises the following components in percentage by mass: the content of transition metal is 8-15%, SiO230-42% of Al2O312-20% of K2O≦1.3%、MgO≦0.8%；
b. Taking a certain amount of waste-based powder prepared in the step a, adding a certain amount of HNO prepared in the step a3Mixing the solution, waste-based powder and HNO3The mixing ratio of the solution is (1-3) g: 25mL, stirring for at least 30min, adding a certain amount of NaOH solution prepared in the step a to control the pH of the solution to be 8-9, stirring for at least 30min, and centrifuging to obtain a solid for later use;
c. putting the solid obtained in the step b into an oven with the temperature not higher than 100 ℃ for drying treatment for 5-8h, transferring the solid into a muffle furnace after the solid is dried, starting a muffle furnace temperature programming system, carrying out high-temperature treatment for at least 3h at the constant temperature not higher than 400 ℃, and taking out the solid material for later use;
step 2: the method comprises the following steps of preparing a chemically bonded ceramic catalyst by waste base mixing, and obtaining an integral catalyst by a forming process:
(1) preparing an auxiliary excitant according to the mass ratio K2O:Al2O3:SO3:H2O =1:1.2:0.3:1.5, mixing the medicines, and uniformly stirring to obtain an auxiliary exciting agent for later use;
(2) and additionally, mixing a certain amount of waste base materials with the solid materials prepared by the activation treatment in the step 1, wherein the adopted waste base materials comprise the following components in percentage by mass: SiO 2225-33% of Al2O39-17 percent of CaO, 38-48 percent of CaO and SO3At the mass ratio of less than or equal to 2 percent, controlling the mixing mass ratio to be (2.3-3.1):1 to obtain a mixed raw material, then adding CaO in an amount of 5 percent by mass relative to the mixed raw material based on the total amount of the mixed raw material, adding the auxiliary activator prepared in the step (1) in an amount of 3 percent by mass relative to the mixed raw material, and adding35% of H relative to the mass ratio of the mixed raw materials2O, uniformly mixing the materials to prepare a ball-milling mixed material, then putting the ball-milling mixed material into a ball mill for ball milling for at least 10min, and putting the obtained ball-milled solid material into a mould for molding;
(3) placing the mould into which the solid material subjected to ball milling in the step (2) is placed in a chamber for standing for at least 8 hours, and spraying a small amount of water to the surface of the solid material in the mould at intervals of at most 2 hours to keep the solid material moist;
(4) putting the mould and the solid material in the step (3) into a tubular furnace, introducing steam into the tubular furnace, controlling the flow rate of the steam to be not higher than 0.2ml/min, starting a tubular furnace temperature programming system, and carrying out constant temperature treatment for at least 22h at the temperature of not higher than 200 ℃;
(5) after the constant temperature treatment procedure in the step (4) is finished, continuously introducing water vapor into the tubular furnace, controlling the flow rate to be not higher than 0.1ml/min, controlling the time of introducing the water vapor to be 2-3h, and performing post-treatment;
(6) and (4) after the post-treatment in the step (4) is finished, taking out the mold and the solid material from the tube furnace, drying the mold and the solid material at room temperature, and demolding the solid material after drying to obtain the monolithic catalyst.
2. The method for preparing a monolithic catalyst from waste-based materials as claimed in claim 1, wherein the axial compressive strength of the prepared monolithic catalyst in step 2 is 220-280N/cm2The radial compressive strength of the material is 80-100N/cm2The abrasion resistance is 0.080-0.10%/kg; the number of fine cracks on the single-side end face of the prepared monolithic catalyst is 3-7, the crack width is less than or equal to 0.040mm, and the crack length is 25-33% of the total length of the catalyst.
3. The method of claim 1, wherein in the step 2, a catalyst active layer is formed on the surface of the prepared monolithic catalyst, and when active components on the surface of the monolithic catalyst are removed during the use process, the components inside the monolithic catalyst can be exposed to form a mesoporous-type catalytic active interface.
4. The method for preparing a monolithic catalyst from waste based materials as claimed in claim 1, wherein in the step 2, the substance-to-substance connection in the prepared monolithic catalyst material is mainly ionic bond and covalent bond, and is assisted by hydrogen bond and van der waals force.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811429647.0A CN109621944B (en) | 2018-11-28 | 2018-11-28 | Method for preparing monolithic catalysts using waste-based materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811429647.0A CN109621944B (en) | 2018-11-28 | 2018-11-28 | Method for preparing monolithic catalysts using waste-based materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109621944A CN109621944A (en) | 2019-04-16 |
| CN109621944B true CN109621944B (en) | 2021-12-03 |
Family
ID=66069651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811429647.0A Active CN109621944B (en) | 2018-11-28 | 2018-11-28 | Method for preparing monolithic catalysts using waste-based materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109621944B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209490B (en) * | 2020-07-24 | 2022-03-01 | 东莞理工学院 | Improving O content in modified domestic garbage incinerator slag3Method for treating urban black smelly water effect |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526676A (en) * | 2003-09-23 | 2004-09-08 | 昆明理工大学 | CBC composite material made of industrial slag and its production process |
| AU2004283644A1 (en) * | 2003-10-29 | 2005-05-06 | Doxa Ab | A two-step system for improved initial and final characteristics of a biomaterial |
| CN101237930A (en) * | 2005-03-08 | 2008-08-06 | 瓦斯技术研究所 | Method for producing catalytically-active materials |
| CN106582596A (en) * | 2016-12-28 | 2017-04-26 | 湖北思搏盈环保科技有限公司 | Method for forming fly-ash-based honeycomb type denitration catalyst ceramic carrier |
| CN107754799A (en) * | 2017-11-23 | 2018-03-06 | 北京工业大学 | A kind of method that ferro-silicon slag prepares medium temperature demercuration catalysis material |
-
2018
- 2018-11-28 CN CN201811429647.0A patent/CN109621944B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526676A (en) * | 2003-09-23 | 2004-09-08 | 昆明理工大学 | CBC composite material made of industrial slag and its production process |
| AU2004283644A1 (en) * | 2003-10-29 | 2005-05-06 | Doxa Ab | A two-step system for improved initial and final characteristics of a biomaterial |
| CN101237930A (en) * | 2005-03-08 | 2008-08-06 | 瓦斯技术研究所 | Method for producing catalytically-active materials |
| CN106582596A (en) * | 2016-12-28 | 2017-04-26 | 湖北思搏盈环保科技有限公司 | Method for forming fly-ash-based honeycomb type denitration catalyst ceramic carrier |
| CN107754799A (en) * | 2017-11-23 | 2018-03-06 | 北京工业大学 | A kind of method that ferro-silicon slag prepares medium temperature demercuration catalysis material |
Non-Patent Citations (2)
| Title |
|---|
| 用工业废渣制备CBC复合材料基础研究;张召述;《中国优秀博士学位论文全文数据库 工程科技I辑》;20071231(第5期);第28页最后1段，第46页图2.1，第64页 * |
| 黄磷炉渣制备化学键合陶瓷复合材料工艺研究;周亮亮 等;《化工矿物与加工》;20070731(第7期);第1.2 CBC复合材料、3 研究内容、图1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109621944A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111138167B (en) | Ceramic catalyst taking red mud waste residue as carrier and preparation method and application thereof | |
| CN101347722B (en) | Catalyst for denitration by SCR method with low cost and preparation method thereof | |
| CN112142491B (en) | Integrated oxygen carrier for chemical looping hydrogen production, preparation method, hydrogen production system and method | |
| CN101327928A (en) | Calcium carbide production method | |
| CN103641507B (en) | Zeolite-attapulgite composite honeycomb body and preparation method thereof | |
| CN102728346B (en) | MnO2-TiO2 carbon nanotube-porous inorganic ceramic membrane low-temperature catalytic denitrification self-cleaning material and its preparation method | |
| WO2021012737A1 (en) | Reforming hydrogen production catalyst using waste vanadium-titanium denitration catalyst as raw material and preparation method therefor | |
| CN109621944B (en) | Method for preparing monolithic catalysts using waste-based materials | |
| CN108822073B (en) | Preparation method and application of vinyl sulfate | |
| CN110882691B (en) | Cordierite supported medium-temperature denitration catalyst and preparation method thereof | |
| CN108837823A (en) | A kind of perovskite type catalyst and its monoblock type forming method and application | |
| CN114632520A (en) | Preparation method and application of aluminum-carbon composite advanced oxidation catalyst | |
| CN110624538A (en) | Manganese-based denitration catalyst and production process thereof | |
| CN103041810B (en) | Cellulosic ethanol wastewater treatment catalyst, preparation method thereof and wastewater treatment method | |
| CN114011400A (en) | Preparation method of acid system waste incineration SCR denitration catalyst and prepared denitration catalyst | |
| CN101301607B (en) | High-efficiency energy-saving combustion supporting catalyst | |
| CN108404966B (en) | Coke oven flue gas low-temperature denitration catalyst and preparation method thereof | |
| CN112191267A (en) | Honeycomb catalyst for removing dioxin in flue gas through catalytic oxidation and preparation method thereof | |
| CN115007163B (en) | Preparation method of supported copper-bismuth catalyst and supported copper-bismuth catalyst | |
| CN106669728A (en) | Integral-type low-temperature SCR denitration catalyst and preparation method thereof | |
| CN114042473B (en) | Method for improving mechanical strength of binder-free integral molecular sieve based catalyst | |
| CN114345245A (en) | Fixed bed chemical chain reaction device and integral oxygen carrier preparation method | |
| CN102608192A (en) | Tubular oxygen sensor and preparation method for same | |
| CN112823876B (en) | Catalyst for preparing MMA (methyl methacrylate) through direct oxidative esterification and preparation method thereof | |
| CN109516792A (en) | A kind of preparation method of gas purification porous ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |