CN115999525A - SCR denitration catalyst carrier and preparation method thereof - Google Patents
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Abstract
The invention is suitable for the technical field of denitration catalysts, and provides an SCR denitration catalyst carrier and a preparation method thereof, wherein the SCR denitration catalyst carrier prepared by the invention is honeycomb-shaped, the aperture ratio is 40% -85%, the honeycomb-shaped carrier can increase the coating area of the catalyst, and meanwhile, when flue gas is treated, the flue gas passes through honeycomb-shaped pores to increase the reaction area, and the preparation raw materials are natural minerals, adhesives and water, and the preparation method comprises the following steps: 1. mixing natural minerals with a binder, and then adding water to uniformly mix to obtain a solid mixture; 2. mixing and kneading the solid mixture by a kneading machine, and then carrying out coarse refining and sieving, ageing, refining and sieving in sequence to obtain pug; 3. extruding the pug through an extruder to obtain SCR denitration catalyst carrier green blanks, and drying and shaping the SCR denitration catalyst carrier green blanks through a drying device; 4. and firing and cutting the dried and shaped SCR denitration catalyst carrier green embryo to finally obtain a finished product of the SCR denitration catalyst carrier.
Description
Technical Field
The invention is suitable for the technical field of denitration catalysts, and provides an SCR denitration catalyst carrier and a preparation method thereof.
Background
Nitrogen oxides are a typical atmospheric pollutant, which is the basis for the formation of nitric acid type acid rain and ozone (O) 3 ) And secondary fine Particulate Matter (PM) 2.5 ) And also have a strong toxicity per se. The emission of nitrogen oxides in large quantities not only can lead to the reduction of the quality of the ambient air, but also can seriously affect the health of human bodies. Against the increasingly severe pollution situation, the state intensively releases a large number of policies and standards to strictly control the emission of nitrogen oxides. Through the development in recent years, the emission of nitrogen oxides in the power industry is strictly controlled, and the emission of nitrogen oxides in non-electric industries such as steel, cement, coking, glass and the like is the treatment focus in the current stage.
The Selective Catalytic Reduction (SCR) denitration is used as the most widely-applied and most mature flue gas denitration technology, and the technical core is a denitration catalyst. Currently, commercial SCR denitration catalyst in non-electric industry is basically V 2 O 5 -WO 3 /TiO 2 The system is integrally formed into a catalyst. The catalyst has the defect that the active site in the catalyst cannot be effectively utilized in the life cycle, and SO 2 The method is characterized in that a coating type denitration catalyst is derived aiming at the problems, the coating type denitration catalyst is a novel honeycomb type denitration catalyst, active substances are coated on a honeycomb type carrier to form a multi-layer structure denitration catalyst, the carrier is mostly honeycomb cordierite, a molecular sieve or a metal carrier, the multi-layer structure coating type denitration catalyst can effectively reduce the use of rare catalyst materials, and meanwhile, the catalyst can be ensured to have enough nitrogen oxide removal activity, and the coating is carried outThe SCR denitration catalyst is widely applied to the treatment of nitrogen oxides in automobile exhaust, and due to the problem of carrier cost, the application of the coated SCR denitration catalyst in the field of industrial flue gas treatment is very few, and the SCR denitration catalyst carrier applicable to the field of industrial flue gas treatment is not developed pertinently at present, so that the wide commercial application of the coated SCR catalyst in the field of industrial flue gas nitrogen oxides treatment is restricted.
Therefore, in order to further popularize the application of the SCR denitration catalyst in the field of industrial flue gas treatment, development of a high-strength and wear-resistant carrier suitable for preparing the SCR denitration catalyst by a coating method is urgently needed, and the high catalytic activity, the wider reaction temperature range and the low SO are developed by combining a coating technology 2 The SCR denitration catalyst with high oxidation rate and better poisoning resistance provides basic support for the increasingly strict emission control requirements of nitrogen oxides in the non-electric industry.
Disclosure of Invention
The invention provides an SCR denitration catalyst carrier and a preparation method thereof, wherein common natural mineral particles are used as raw materials, and the SCR denitration catalyst carrier with high mechanical strength, abrasion resistance and high aperture ratio is prepared by treatment and sintering.
The SCR denitration catalyst carrier is prepared from natural minerals, an adhesive and water, wherein the natural minerals are a mixture formed by any combination of one or more of bentonite, columnar clay, kaolin, red clay, attapulgite and quartz sand, and the adhesive is a mixture formed by any combination of one or more of hydroxypropyl methylcellulose, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyacrylamide, phenolic resin and polyimide resin.
Preferably, the SCR denitration catalyst carrier comprises the following raw materials in parts by weight: 100 parts of natural minerals, 5-10 parts of binders and 25-40 parts of water.
Preferably, the carrier of the SCR denitration catalyst is in a honeycomb shape, the aperture ratio is 40% -85%, the honeycomb-shaped carrier can increase the coating area of the catalyst, and meanwhile, when the flue gas is treated, the flue gas passes through the honeycomb-shaped pores, so that the reaction area can be increased.
Preferably, the median particle size of the natural minerals is 3-15 microns, and the main reason for the preferred particle size is to ensure that the performances of the SCR denitration catalyst carrier in the scheme are similar everywhere, and the situation of different strength of each position is avoided.
The preparation method of the SCR denitration catalyst carrier comprises the following steps:
s1, mixing natural minerals with a binder, and then adding water to uniformly mix to obtain a solid mixture;
s2, mixing and kneading the solid mixture by a mud kneader, and then obtaining mud materials after coarse refining, sieving, ageing, refining and sieving in sequence, wherein the two sieving can enable the mixture to be more uniform as far as possible and fully mixed;
s3, extruding and molding the pug through an extruder to obtain an SCR denitration catalyst carrier green body, and drying and shaping the SCR denitration catalyst carrier green body through a drying device;
s4, the SCR denitration catalyst carrier green blank after drying and shaping is finally obtained into an SCR denitration catalyst carrier finished product after firing and cutting, the firing is the most important process for increasing the strength, and the strength of the carrier finished product after firing can be greatly increased to reach the expected design standard.
Preferably, in the step S2, the mixing and mud kneading time is 20-80 minutes, the specification of a filter screen used for coarse mixing and sieving is 40-90 meshes, the aging time is 12-24 hours, and the specification of a filter screen used for refining and sieving is 100-150 meshes.
Preferably, in the step S3, the drying temperature of the SCR denitration catalyst carrier green embryo is 100-150 ℃ and the drying time is 8-12 hours.
Preferably, in the step S4, the temperature is 600-1400 ℃ in the sintering process of the SCR denitration catalyst carrier green embryo, the sintering time is 6-18 hours, the heating rate is 50-100 ℃/hour, the sintering is performed in a gradual heating mode, the problem of product breakage caused by short-time high-temperature sintering can be reduced, and the yield is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the scheme provided by the invention can prepare the SCR denitration catalyst carrier which can apply the coated SCR denitration catalyst to the field of industrial flue gas treatment, the honeycomb SCR denitration catalyst carrier is prepared by taking natural minerals as raw materials through a series of processes, and the SCR denitration catalyst is attached in honeycomb holes through a coating method, SO that the problems that the internal active site of the catalyst cannot be effectively utilized and the SO2 oxidation rate is high in the life cycle of the integrally formed SCR denitration catalyst in flue gas treatment are effectively solved;
2. the SCR denitration catalyst carrier is mainly prepared from natural minerals, the types of the used minerals have various combination modes, the formula can be timely adjusted according to the cost of each component, the sources of goods and other factors so as to keep the most economical production mode, and the SCR denitration catalyst carrier has good economic benefits.
Drawings
Fig. 1 is a graph comparing components and performance data of the SCR denitration catalyst carrier and the preparation method thereof in example 1 to example 6 in the present invention.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
The embodiment 1, an SCR denitration catalyst carrier, the shape is honeycomb, the aperture ratio is 76.5%, the inner wall thickness is 0.85 mm, the outer wall thickness is 1.34 mm, the aperture is 6.25 mm, the SCR denitration catalyst carrier is prepared from natural minerals, adhesive and water as raw materials, the natural minerals are a mixture of columnar clay, kaolin and quartz sand, the median particle diameter of the columnar clay, kaolin and quartz sand is 3-15 microns, the adhesive is polyethylene glycol, and the raw materials are as follows: 50 parts of columnar clay, 45 parts of kaolin, 5 parts of quartz sand, 5 parts of polyethylene glycol and 30 parts of water.
The preparation method of the SCR denitration catalyst carrier in the embodiment comprises the following steps:
s1, mixing natural minerals with a binder, and then adding water to uniformly mix to obtain a solid mixture;
s2, mixing and kneading the solid mixture by a mud kneader, and then carrying out coarse refining and sieving, ageing and refining and sieving in sequence to obtain mud, wherein the mud kneading time is 30 minutes, the specification of a filter screen used for coarse refining and sieving is 40-90 meshes, the ageing time is 20 hours, and the specification of a filter screen used for refining and sieving is 100-150 meshes;
s3, extruding and molding the pug through an extruder to obtain an SCR denitration catalyst carrier blank, and drying and shaping the SCR denitration catalyst carrier blank through a drying device, wherein the drying temperature of the drying and shaping is 100 ℃, and the drying time is 12 hours;
s4, firing and cutting the dried and shaped SCR denitration catalyst carrier green embryo to finally obtain a finished product of the SCR denitration catalyst carrier, wherein the firing temperature is 800 ℃, the firing time is 10 hours, and the heating rate is 80 ℃/hour.
The SCR denitration catalyst carrier prepared by the method and the formula can be obtained through experimental tests:
1. the test shows that the transverse mechanical strength is 2.4mPa and the longitudinal mechanical strength is 5.6mPa;
2. the test shows that the carrier wear rate is 0.015%/kg. (Experimental conditions: abrasive concentration 50g/m 3 The flow rate of the flue gas is 15m/s, the incidence angle of the flue gas is 0 degree, the particle size of the abradant is 90 mu m, and the test time is 2h. )
The embodiment 2 is an SCR denitration catalyst carrier, which is in a honeycomb shape, has an aperture ratio of 76.5%, an inner wall thickness of 0.85 mm, an outer wall thickness of 1.34 mm and a pore diameter of 6.25 mm, and is prepared from natural minerals, a binder and water as raw materials, wherein the natural minerals are a mixture of bentonite, kaolin and quartz sand, the median particle diameter of the bentonite, the kaolin and the quartz sand is 3-15 microns, the binder is polyacrylamide, and the raw materials are as follows: 45 parts of bentonite, 45 parts of kaolin, 10 parts of quartz sand, 8 parts of polyacrylamide and 32 parts of water.
The preparation method of the SCR denitration catalyst carrier in the embodiment comprises the following steps:
s1, mixing natural minerals with a binder, and then adding water to uniformly mix to obtain a solid mixture;
s2, mixing and kneading the solid mixture by a mud kneader, and then carrying out coarse refining and sieving, ageing and refining and sieving in sequence to obtain mud, wherein the mud kneading time is 30 minutes, the specification of a filter screen used for coarse refining and sieving is 40-90 meshes, the ageing time is 24 hours, and the specification of a filter screen used for refining and sieving is 100-150 meshes;
s3, extruding and molding the pug through an extruder to obtain an SCR denitration catalyst carrier blank, and drying and shaping the SCR denitration catalyst carrier blank through a drying device, wherein the drying temperature of the drying and shaping is 120 ℃, and the drying time is 10 hours;
s4, firing and cutting the dried and shaped SCR denitration catalyst carrier green embryo to finally obtain a finished product of the SCR denitration catalyst carrier, wherein the firing temperature is 1000 ℃, the firing time is 8 hours, and the heating rate is 100 ℃/hour.
The SCR denitration catalyst carrier prepared by the method and the formula can be obtained through experimental tests:
1. the test shows that the transverse mechanical strength is 3.8mPa and the longitudinal mechanical strength is 7.2mPa;
2. the test shows that the carrier wear rate is 0.011%/kg. (Experimental conditions: abrasive concentration 50g/m 3 The flow rate of the flue gas is 15m/s, the incidence angle of the flue gas is 0 degree, the particle size of the abradant is 90 mu m, and the test time is 2h. )
Embodiment 3, an SCR denitration catalyst carrier is in a honeycomb shape, the aperture ratio is 76.5%, the inner wall thickness is 0.85 mm, the outer wall thickness is 1.34 mm, the aperture is 6.25 mm, the SCR denitration catalyst carrier is prepared from natural minerals, a binder and water, wherein the natural minerals are a mixture of bentonite, attapulgite and quartz sand, the median particle size of the bentonite, the attapulgite and the quartz sand is 3-15 microns, the binder is phenolic resin, and the raw materials are as follows: 45 parts of bentonite, 40 parts of attapulgite, 15 parts of quartz sand, 8 parts of phenolic resin and 25 parts of water.
The preparation method of the SCR denitration catalyst carrier in the embodiment comprises the following steps:
s1, mixing natural minerals with a binder, and then adding water to uniformly mix to obtain a solid mixture;
s2, mixing and kneading the solid mixture by a mud kneader, and then carrying out coarse refining and sieving, ageing and refining sieving in sequence to obtain mud, wherein the mud kneading time is 30 minutes, the specification of a filter screen used for coarse refining and sieving is 40-90 meshes, the ageing time is 18 hours, and the specification of a filter screen used for refining and sieving is 100-150 meshes;
s3, extruding and molding the pug through an extruder to obtain an SCR denitration catalyst carrier blank, and drying and shaping the SCR denitration catalyst carrier blank through a drying device, wherein the drying temperature of the drying and shaping is 110 ℃, and the drying time is 12 hours;
s4, firing and cutting the dried and shaped SCR denitration catalyst carrier green embryo to finally obtain a finished product of the SCR denitration catalyst carrier, wherein the firing temperature is 600 ℃, the firing time is 12 hours, and the heating rate is 50 ℃/hour.
The SCR denitration catalyst carrier prepared by the method and the formula can be obtained through experimental tests:
1. the test shows that the transverse mechanical strength is 2mPa and the longitudinal mechanical strength is 3.2mPa;
2. the test gave a carrier wear rate of 0.023%/kg. (Experimental conditions: abrasive concentration 50g/m 3 The flow rate of the flue gas is 15m/s, the incidence angle of the flue gas is 0 degree, the particle size of the abradant is 90 mu m, and the test time is 2h. )
The embodiment 4 is an SCR denitration catalyst carrier, which is in a honeycomb shape, has an aperture ratio of 76.5%, an inner wall thickness of 0.85 mm, an outer wall thickness of 1.34 mm and a pore diameter of 6.25 mm, and is prepared from natural minerals, a binder and water as raw materials, wherein the mixture of the natural minerals bentonite, kaolin and quartz sand has a median particle diameter of 3-15 microns, the binder is polyacrylamide, and the raw materials are as follows: 40 parts of bentonite, 40 parts of kaolin, 20 parts of quartz sand, 6 parts of polyacrylamide and 35 parts of water.
The preparation method of the SCR denitration catalyst carrier in the embodiment comprises the following steps:
s1, mixing natural minerals with a binder, and then adding water to uniformly mix to obtain a solid mixture;
s2, mixing and kneading the solid mixture by a mud kneader, and then carrying out coarse refining and sieving, ageing and refining and sieving in sequence to obtain mud, wherein the mud kneading time is 30 minutes, the specification of a filter screen used for coarse refining and sieving is 40-90 meshes, the ageing time is 20 hours, and the specification of a filter screen used for refining and sieving is 100-150 meshes;
s3, extruding and molding the pug through an extruder to obtain an SCR denitration catalyst carrier blank, and drying and shaping the SCR denitration catalyst carrier blank through a drying device, wherein the drying temperature of the drying and shaping is 120 ℃, and the drying time is 10 hours;
s4, firing and cutting the dried and shaped SCR denitration catalyst carrier green embryo to finally obtain a finished product of the SCR denitration catalyst carrier, wherein the firing temperature is 800 ℃, the firing time is 10 hours, and the heating rate is 80 ℃/hour.
The SCR denitration catalyst carrier prepared by the method and the formula can be obtained through experimental tests:
1. the test shows that the transverse mechanical strength is 3.5mPa and the longitudinal mechanical strength is 6.4mPa;
2. the test gave a carrier wear rate of 0.007%/kg. (Experimental conditions: abrasive concentration 50g/m 3 The flow rate of the flue gas is 15m/s, the incidence angle of the flue gas is 0 degree, the particle size of the abradant is 90 mu m, and the test time is 2h. )
The preparation method of the SCR denitration catalyst carrier in the embodiment comprises the following steps:
s1, mixing natural minerals with a binder, and then adding water to uniformly mix to obtain a solid mixture;
s2, mixing and kneading the solid mixture by a mud kneader, and then carrying out coarse refining and sieving, ageing and refining sieving in sequence to obtain mud, wherein the mud kneading time is 30 minutes, the specification of a filter screen used for coarse refining and sieving is 40-90 meshes, the ageing time is 22 hours, and the specification of a filter screen used for refining and sieving is 100-150 meshes;
s3, extruding and molding the pug through an extruder to obtain an SCR denitration catalyst carrier blank, and drying and shaping the SCR denitration catalyst carrier blank through a drying device, wherein the drying temperature of the drying and shaping is 100 ℃, and the drying time is 11 hours;
s4, firing and cutting the dried and shaped SCR denitration catalyst carrier green embryo to finally obtain a finished product of the SCR denitration catalyst carrier, wherein the firing temperature is 600 ℃, the firing time is 18 hours, and the heating rate is 50 ℃/hour.
The SCR denitration catalyst carrier prepared by the method and the formula can be obtained through experimental tests:
1. the test shows that the transverse mechanical strength is 2.2mPa and the longitudinal mechanical strength is 3.5mPa;
2. the test shows that the abrasion rate of the carrier is 0.016%/kg. (Experimental conditions: abrasive concentration 50g/m 3 The flow rate of the flue gas is 15m/s, the incidence angle of the flue gas is 0 degree, the particle size of the abradant is 90 mu m, and the test time is 2h. )
The above 5 examples all meet the requirements that in the design, the transverse mechanical strength is more than or equal to 1.5mPa, the longitudinal mechanical strength is more than or equal to 2.5mPa and the abrasion rate is less than or equal to 0.05%/kg, and the abrasion resistance of the SCR denitration catalyst carrier prepared by the scheme of the example 4 is optimal and the mechanical strength also far exceeds the design index, so that the comprehensive performance and the durability are achieved, and the scheme of the example 4 is the optimal example of the invention.
The above description is only of the preferred embodiments of the present invention, and any person skilled in the art may modify the present invention or make modifications to the present invention equivalent thereto using the technical solutions described above. Therefore, any simple modification or equivalent made according to the technical solution of the present invention falls within the scope of the protection claimed by the present invention.
Claims (8)
1. The SCR denitration catalyst carrier is characterized by being prepared from natural minerals, an adhesive and water, wherein the natural minerals are a mixture formed by any combination of one or more of bentonite, columnar clay, kaolin, red clay, attapulgite and quartz sand, and the adhesive is a mixture formed by any combination of one or more of hydroxypropyl methylcellulose, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polyacrylamide, phenolic resin and polyimide resin.
2. The SCR denitration catalyst carrier as claimed in claim 1, wherein the SCR denitration catalyst carrier comprises the following raw materials in parts by mass: 100 parts of natural minerals, 5-10 parts of binders and 25-40 parts of water.
3. The SCR denitration catalyst carrier as claimed in claim 2, wherein the SCR denitration catalyst carrier is in a honeycomb shape, and the aperture ratio is 40% -85%.
4. The SCR denitration catalyst carrier of claim 2, wherein the natural mineral has a median particle size of 3 microns to 15 microns.
5. The method for preparing the SCR denitration catalyst carrier as claimed in any one of claims 1 to 4, characterized in that the aforementioned preparation method comprises the steps of:
s1, mixing natural minerals with a binder, and then adding water to uniformly mix to obtain a solid mixture;
s2, mixing and kneading the solid mixture by a mud kneader, and then carrying out coarse refining and sieving, ageing, refining and sieving in sequence to obtain mud materials;
s3, extruding and molding the pug through an extruder to obtain an SCR denitration catalyst carrier green body, and drying and shaping the SCR denitration catalyst carrier green body through a drying device;
s4, firing and cutting the dried and shaped SCR denitration catalyst carrier green embryo to finally obtain a finished product of the SCR denitration catalyst carrier.
6. The method for preparing the SCR denitration catalyst carrier according to claim 5, wherein in the step S2, the time for mixing and kneading mud is 20-80 minutes, the specification of a filter screen used for rough mixing and sieving is 40-90 meshes, the ageing time is 12-24 hours, and the specification of a filter screen used for refining and sieving is 100-150 meshes.
7. The method for preparing an SCR denitration catalyst carrier according to claim 5, wherein the drying temperature of the green embryo of the SCR denitration catalyst carrier in step S3 is 100-150 ℃ and the drying time is 8-12 hours.
8. The method for preparing an SCR denitration catalyst carrier according to claim 5, wherein the temperature in the firing process of the SCR denitration catalyst carrier green body in step S4 is 600 ℃ to 1400 ℃, the firing time is 6 hours to 18 hours, and the heating rate is 50 ℃/hour to 100 ℃/hour.
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