CN111085216A - Preparation method of efficient rare earth tailing-based SCR catalyst - Google Patents
Preparation method of efficient rare earth tailing-based SCR catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-efficiency rare earth tailing-based SCR catalyst, which utilizes metal oxides such as Fe, RE, Mn and the like in rare earth tailings as main active substances, adopts a physical means to add natural manganese ore or pyrite as an auxiliary agent, and adds pseudo-boehmite (or aluminum nitrate) or TiO2The denitration catalyst with low cost, short preparation process, environmental protection and high added value is prepared by loading; the prepared catalyst shows good catalytic activity; the method reduces resource waste and environmental pollution; provides new high value-added utilization of the bayan obo rare earth tailingsThe idea and scientific basis.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a high-efficiency rare earth tailing-based SCR catalyst.
Background
The main energy consumed in China is coal, and clean energy such as natural gas, hydropower, nuclear power, wind power and the like only accounts for 20 percent; the main utilization form of coal in China is direct combustion, a large amount of NOx can be released in the combustion of fossil fuels such as coal and the like, nitric oxide is combined with water in the air and finally converted into nitric acid and nitrate, and the nitric acid is one of the causes of acid rain; acid rain not only damages the development of social economy and the ecological system, but also seriously affects the health and normal life of human beings.
China is a big rare earth country, and the reserves of rare earth ores account for 23 percent of the world and are at the top of the world; the bayan obo ore is a rare large-scale multi-metal symbiotic ore deposit in the world, contains rich resources such as rare earth, iron, niobium, fluorite and the like, and is a first rare earth ore resource in the world and a second niobium ore resource base in the world; since the development of the bayan obo ore deposit, the recovery rate of valuable components is low, and a large amount of resources are totally used as tailing piles and exist in a tailing dam; the annual throughput of Baotou iron and steel works (ladle steel) is already over 1000 ten thousand tons; with the concomitant discharge of large quantities of tailings; the stockpiled tailings in a tailing pond exceed 15 hundred million tons, and a large amount of waste water exists; since the mine is put into operation, the main ore bodies are treated as single iron ores, and the comprehensive recovery rate of the rare earth is only about 10 percent; a large amount of rare earth minerals are discarded into tailings; along with the development and utilization of a large amount of rare earth mineral resources, ores are increasingly deficient, and rare earth tailings as secondary resources are valued by countries in the world for reutilization; the application aims to explore the preparation of the denitration catalyst which is low in cost, short in preparation process, green, environment-friendly and high in added value by taking the rare earth tailings as raw materials.
Disclosure of Invention
The invention aims to provide a preparation method of a high-efficiency rare earth tailing-based SCR catalyst, which utilizes Fe, RE and RE in rare earth tailingsMn and other metal oxides as main active matter, adding natural manganese ore or pyrite as assistant, adding pseudo-boehmite (or aluminium nitrate) or TiO2The denitration catalyst with low cost, short preparation process, environmental protection and high added value is prepared by loading; the prepared catalyst shows good catalytic activity; the method reduces resource waste and environmental pollution; provides a new idea and scientific basis for the high value-added utilization of the bayan obo rare earth tailings.
The technical scheme adopted by the invention is as follows: a preparation method of a high-efficiency rare earth tailing-based SCR catalyst is characterized by comprising the following steps:
s1: strong magnetic separation: selecting 100-400-mesh rare earth tailings as a raw material; carrying out magnetic separation under the magnetic field intensity of 0.4-2.0T, and dividing the rare earth tailings into magnetic concentrate and magnetic tailings; recycling the obtained magnetic concentrate, and taking the magnetic tailings as a catalyst main body;
s2: adding manganese ore or pyrite: selecting the magnetic separation tailings obtained in the step S1, adding natural manganese ore powder or pyrite powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the manganese ore powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the natural manganese ore or pyrite is 1: 19-19: 1;
s3: adding aluminium source or TiO2: taking the first mixed mineral obtained in the step S2, adding an aluminum source or TiO into the first mixed mineral2Then, putting the mixture into the ball mill again to be ground and mixed uniformly to obtain a second mixed mineral; the first mixed mineral and the aluminum source or TiO2The mass ratio of (A) to (B) is 1: 10-3: 1;
s4, shaping and roasting: adding a proper amount of distilled water into the second mixed mineral obtained in the step S3, and uniformly stirring; then uniformly coating the sample separating sieve, putting the sample separating sieve into an oven, drying and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then, the crucible is used for containing the catalyst and is placed into a muffle furnace for roasting, the roasting temperature is 400-800 ℃, the roasting time is 50-400 min, and the catalyst is taken out to prepare the catalyst.
Further, in step S3, the aluminum source is aluminum nitrate or pseudo-boehmite.
Further, in step S3, TiO is used2Mechanically stirring and mixing the first mineral mixture with adhesive, and adding TiO2。
Application of the catalyst in NH3And NO is 1:1, with O2And N2The catalyst is used as a flue gas denitration catalyst.
The invention has the beneficial effects that: the method of the invention uses metal oxides such as Fe, RE, Mn and the like in rare earth tailings as main active substances, adopts a physical means to add natural manganese ore or pyrite as an auxiliary agent, and adds pseudo-boehmite (or aluminum nitrate) or TiO2The denitration catalyst with low cost, short preparation process, environmental protection and high added value is prepared by loading; the prepared catalyst shows good catalytic activity; the method reduces resource waste and environmental pollution; provides a new idea and scientific basis for the high value-added utilization of the bayan obo rare earth tailings.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments, which are only used for illustrating the technical solution of the present invention and are not limited.
A preparation method of a high-efficiency rare earth tailing-based SCR catalyst comprises the following steps:
s1: strong magnetic separation: selecting 100-400-mesh rare earth tailings as a raw material; carrying out magnetic separation under the magnetic field intensity of 0.4-2.0T, and dividing the rare earth tailings into magnetic concentrate and magnetic tailings; recycling the obtained magnetic concentrate, and taking the magnetic tailings as a catalyst main body; the main purpose of strong magnetic separation is to remove magnetite and highly disperse active components;
s2: adding manganese ore or pyrite: selecting the magnetic separation tailings obtained in the step S1, adding natural manganese ore powder or pyrite powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the manganese ore powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the natural manganese ore or pyrite is 1: 19-19: 1;
s3: adding aluminium source or TiO2: taking the first mixed mineral obtained in the step S2, adding an aluminum source or TiO into the first mixed mineral2Then, putting the mixture into the ball mill again to be ground and mixed uniformly to obtain a second mixed mineral;
the aluminum source is aluminum nitrate or pseudo-boehmite; when an aluminum source is added, the mass ratio of the first mixed mineral to the aluminum source is 1: 10-3: 1; addition of TiO2While the first mixed mineral is mixed with TiO2In a mass ratio of 1:10 to 3:1, and further, TiO is used2The adhesive is mechanically stirred and mixed with the first mixed mineral;
s4, shaping and roasting: adding a proper amount of distilled water into the second mixed mineral obtained in the step S3, and uniformly stirring; then uniformly coating the sample separating sieve, putting the sample separating sieve into an oven, drying and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then, the crucible is used for containing the catalyst and is placed into a muffle furnace for roasting, the roasting temperature is 400-800 ℃, the roasting time is 50-400 min, and the catalyst is taken out to prepare the catalyst.
Application of the catalyst in NH3And NO is 1:1, with O2And N2The catalyst is used as a flue gas denitration catalyst.
Example 1
S1, strong magnetic separation: taking 200-mesh rare earth tailings in the rare earth recovery process as a raw material, carrying out magnetic separation in a strong magnetic separator, wherein the magnetic separation strength is 0.7T, obtaining magnetic concentrate for recycling, and taking the magnetic tailings as a catalyst main body;
s2, adding manganese ore: selecting the magnetic separation tailings obtained in the step S1, adding natural manganese ore powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the manganese ore powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the manganese ore powder is 1: 1;
s3, adding an aluminum source: putting the first mixed mineral obtained in the step S2 into a beaker, and adding an aluminum source into the beaker, wherein the mass ratio of the first mixed mineral to the aluminum source is 2:1, and the aluminum source is aluminum nitrate; then, putting the mixture into the ball mill again to be ground and mixed uniformly to obtain a second mixed mineral;
s4, shaping and roasting: putting the second mixed mineral obtained in the step S3 into a beaker, adding a proper amount of distilled water, and uniformly stirring; then uniformly coating on a 40-mesh sample separating sieve, putting the sample separating sieve into a 100 ℃ oven for drying, and specifically putting into the oven for 20min and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then placing the crucible into a muffle furnace for roasting at 500 ℃ for 120min, and taking out to obtain the catalyst.
Denitration experiments were performed with the prepared catalyst: at NH3And NO is 1:1, introducing O2And use of N in combination2And (3) balancing, wherein the denitration efficiency of the obtained catalyst is 50-99% within the range of 180-300 ℃, and the activity of the catalyst after the manganese ore is added is further improved.
Example 2
S1, strong magnetic separation: taking 325-mesh rare earth tailings in the rare earth recovery process as a raw material, carrying out magnetic separation in a strong magnetic separator, wherein the magnetic separation strength is 0.5T, obtaining magnetic concentrate for recycling, and taking the magnetic tailings as a catalyst main body;
s2, adding pyrite: selecting the magnetic separation tailings obtained in the step S1, adding pyrite powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the pyrite powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the pyrite powder is 3: 1;
s3, adding an aluminum source: putting the first mixed mineral obtained in the step S2 into a beaker, and adding an aluminum source into the beaker, wherein the mass ratio of the first mixed mineral to the aluminum source is 5:1, and the aluminum source is pseudo-boehmite; then, putting the mixture into the ball mill again to be ground and mixed uniformly to obtain a second mixed mineral;
s4, shaping and roasting: putting the second mixed mineral obtained in the step S3 into a beaker, adding a proper amount of distilled water, and uniformly stirring; then uniformly coating on a 40-mesh sample separating sieve, putting the sample separating sieve into a 100 ℃ oven for drying, and specifically putting into the oven for 15min and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then placing the crucible into a muffle furnace for roasting at 400 ℃ for 160min, and taking out to obtain the catalyst.
Denitration experiments were performed with the prepared catalyst: at NH3And NO is 1:1, introducing O2And use of N in combination2And (3) balancing, wherein the denitration efficiency of the obtained catalyst is 50-99% within the range of 180-300 ℃, and the activity of the catalyst is further improved after the pyrite is added.
Example 3
S1, strong magnetic separation: taking 300-mesh rare earth tailings in the rare earth recovery process as a raw material, carrying out magnetic separation in a strong magnetic separator with the magnetic separation strength of 1.0T to obtain magnetic concentrate for recycling, wherein the magnetic tailings are used as a catalyst main body;
s2, adding manganese ore: selecting the magnetic separation tailings obtained in the step S1, adding natural manganese ore powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the manganese ore powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the manganese ore powder is 8: 7;
s3 addition of TiO2: putting the first mixed mineral obtained in the step S2 into a beaker, adding an adhesive, and mechanically stirring and mixing; then adding TiO thereto2The powder is stirred and mixed evenly to obtain a second mixed mineral, a first mixed mineral and TiO2The mass ratio of (A) to (B) is 1: 2;
s4, shaping and roasting: putting the second mixed mineral obtained in the step S3 into a beaker, adding a proper amount of distilled water, and uniformly stirring; then uniformly coating on a 40-mesh sample separating sieve, putting the sample separating sieve into an oven at 85 ℃ for drying, and particularly putting into the oven for 30min and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then placing the crucible into a muffle furnace for roasting at 700 ℃ for 90min, and taking out to obtain the catalyst.
Denitration experiments were performed with the prepared catalyst: at NH3And NO is 1:1, introducing O2And use of N in combination2And (3) balancing, wherein the denitration efficiency of the obtained catalyst is 50-99% within the range of 180-300 ℃, and the activity of the catalyst after the manganese ore is added is further improved.
Example 4
S1, strong magnetic separation: taking 325-mesh rare earth tailings in the rare earth recovery process as a raw material, carrying out magnetic separation in a strong magnetic separator with the magnetic separation strength of 1.6T to obtain magnetic concentrate for recycling, wherein the magnetic tailings are used as a catalyst main body;
s2, adding pyrite: selecting the magnetic separation tailings obtained in the step S1, adding pyrite powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the pyrite powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the pyrite powder is 7: 2;
s3 addition of TiO2: putting the first mixed mineral obtained in the step S2 into a beaker, adding an adhesive, and mechanically stirring and mixing; then adding TiO thereto2The powder is stirred and mixed evenly to obtain a second mixed mineral, a first mixed mineral and TiO2The mass ratio of (A) to (B) is 4: 3;
s4, shaping and roasting: putting the second mixed mineral obtained in the step S3 into a beaker, adding a proper amount of distilled water, and uniformly stirring; then uniformly coating on a 40-mesh sample separating sieve, putting the sample separating sieve into a 120 ℃ oven for drying, and specifically putting into the oven for 10min and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then placing the crucible into a muffle furnace for roasting at the roasting temperature of 450 ℃ for 150min, and taking out the crucible to obtain the catalyst.
Denitration experiments were performed with the prepared catalyst: at NH3And NO is 1:1, introducing O2And use of N in combination2And (3) balancing, wherein the denitration efficiency of the obtained catalyst is 50-99% within the range of 180-300 ℃, and the activity of the catalyst is further improved after the pyrite is added.
Example 5
S1, strong magnetic separation: taking 250-mesh rare earth tailings in the rare earth recovery process as a raw material, carrying out magnetic separation in a strong magnetic separator, wherein the magnetic separation strength is 0.9T, obtaining magnetic concentrate for recycling, and taking the magnetic tailings as a catalyst main body;
s2, adding pyrite: selecting the magnetic separation tailings obtained in the step S1, adding pyrite powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the pyrite powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the pyrite powder is 5: 3;
s3 addition of TiO2: putting the first mixed mineral obtained in the step S2 into a beaker, adding an adhesive, and mechanically stirring and mixing; then adding TiO thereto2The powder is stirred and mixed evenly to obtain a second mixed mineral, a first mixed mineral and TiO2The mass ratio of (A) to (B) is 1: 10;
s4, shaping and roasting: putting the second mixed mineral obtained in the step S3 into a beaker, adding a proper amount of distilled water, and uniformly stirring; then uniformly coating on a 40-mesh sample separating sieve, putting the sample separating sieve into an oven at 80 ℃ for drying, and particularly putting into the oven for 40min and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then placing the crucible into a muffle furnace for roasting at the roasting temperature of 600 ℃ for 110min, and taking out the crucible to obtain the catalyst.
Denitration experiments were performed with the prepared catalyst: at NH3And NO is 1:1, introducing O2And use of N in combination2And (3) balancing, wherein the denitration efficiency of the obtained catalyst is 50-99% within the range of 180-300 ℃, and the activity of the catalyst is further improved after the pyrite is added.
Example 6
S1, strong magnetic separation: taking 300-mesh rare earth tailings in the rare earth recovery process as a raw material, carrying out magnetic separation in a strong magnetic separator with the magnetic separation strength of 1.2T to obtain magnetic concentrate for recycling, wherein the magnetic tailings are used as a catalyst main body;
s2, adding manganese ore: selecting the magnetic separation tailings obtained in the step S1, adding natural manganese ore powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the manganese ore powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the manganese ore powder is 2: 5;
s3 addition of TiO2: putting the first mixed mineral obtained in the step S2 into a beaker, adding an adhesive, and mechanically stirring and mixing; then adding TiO thereto2The powder is stirred and mixed evenly to obtain a second mixed mineral, a first mixed mineral and TiO2The mass ratio of (A) to (B) is 5: 8;
s4, shaping and roasting: putting the second mixed mineral obtained in the step S3 into a beaker, adding a proper amount of distilled water, and uniformly stirring; then uniformly coating on a 40-mesh sample separating sieve, putting the sample separating sieve into a 75 ℃ oven for drying, and particularly putting into a 50min oven and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then placing the crucible into a muffle furnace for roasting at 800 ℃ for 60min, and taking out to obtain the catalyst.
Denitration experiments were performed with the prepared catalyst: at NH3And NO is 1:1, introducing O2And use of N in combination2And (3) balancing, wherein the denitration efficiency of the obtained catalyst is 50-99% within the range of 180-300 ℃, and the activity of the catalyst after the manganese ore is added is further improved.
Example 7
S1, strong magnetic separation: taking 325-mesh rare earth tailings in the rare earth recovery process as a raw material, carrying out magnetic separation in a strong magnetic separator, wherein the magnetic separation strength is 1.8T, obtaining magnetic concentrate for recycling, and taking the magnetic tailings as a catalyst main body;
s2, adding pyrite: selecting the magnetic separation tailings obtained in the step S1, adding pyrite powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the pyrite powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the pyrite powder is 7: 2;
s3 addition of TiO2: putting the first mixed mineral obtained in the step S2 into a beaker, adding an adhesive, and mechanically stirring and mixing; then adding TiO thereto2The powder is stirred and mixed evenly to obtain a second mixed mineral, a first mixed mineral and TiO2The mass ratio of (A) to (B) is 3: 10;
s4, shaping and roasting: putting the second mixed mineral obtained in the step S3 into a beaker, adding a proper amount of distilled water, and uniformly stirring; then uniformly coating on a 40-mesh sample separating sieve, putting the sample separating sieve into a 100 ℃ oven for drying, and specifically putting into the oven for 20min and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then placing the crucible into a muffle furnace for roasting at the roasting temperature of 600 ℃ for 110min, and taking out the crucible to obtain the catalyst.
Denitration experiments were performed with the prepared catalyst: at NH3And NO is 1:1Under the condition, introducing O2And use of N in combination2And (3) balancing, wherein the denitration efficiency of the obtained catalyst is 50-99% within the range of 180-300 ℃, and the activity of the catalyst is further improved after the pyrite is added.
The method of the invention uses metal oxides such as Fe, RE, Mn and the like in rare earth tailings as main active substances, adopts a physical means to add natural manganese ore or pyrite as an auxiliary agent, and adds pseudo-boehmite (or aluminum nitrate) or TiO2The denitration catalyst with low cost, short preparation process, environmental protection and high added value is prepared by loading; the prepared catalyst shows good catalytic activity; the method reduces resource waste and environmental pollution; provides a new idea and scientific basis for the high value-added utilization of the bayan obo rare earth tailings.
Compared with the method for preparing the denitration catalyst by taking the rare earth tailings as the raw materials, which are disclosed by invention patents CN109821523A and CN109821522A previously applied by the inventor, the method disclosed by the invention is different from the method in that natural manganese ore or pyrite is added on the basis of changing the operation conditions, so that the catalytic effect of the catalyst is further improved, and TiO is added at the same time2Is a catalyst carrier; fe. Metal oxides such as RE, Mn and the like show good catalytic activity; the iron oxide has the characteristics of stability, low price and the like, and is widely applied to the field of catalysis in recent years, and the single iron oxide has weak high-temperature oxidation-reduction capability, so that the iron oxide has higher value only by adding an auxiliary agent in the catalysis process.
Although the present invention has been described in detail with reference to the foregoing examples, it will be apparent to one skilled in the art that various changes in the embodiments and/or modifications of the embodiments and/or portions thereof may be made, and all changes, equivalents, and modifications that fall within the spirit and scope of the invention are therefore intended to be embraced by the appended claims.
Claims (4)
1. A preparation method of a high-efficiency rare earth tailing-based SCR catalyst is characterized by comprising the following steps:
s1: strong magnetic separation: selecting 100-400-mesh rare earth tailings as a raw material; carrying out magnetic separation under the magnetic field intensity of 0.4-2.0T, and dividing the rare earth tailings into magnetic concentrate and magnetic tailings; recycling the obtained magnetic concentrate, and taking the magnetic tailings as a catalyst main body;
s2: adding manganese ore or pyrite: selecting the magnetic separation tailings obtained in the step S1, adding natural manganese ore powder or pyrite powder into the magnetic separation tailings, and grinding the mixture in a ball mill to uniformly mix the magnetic separation tailings and the manganese ore powder to obtain a first mixed mineral; the mass ratio of the magnetic separation tailings to the natural manganese ore or pyrite is 1: 19-19: 1;
s3: adding aluminium source or TiO2: taking the first mixed mineral obtained in the step S2, adding an aluminum source or TiO into the first mixed mineral2Then, putting the mixture into the ball mill again to be ground and mixed uniformly to obtain a second mixed mineral; the first mixed mineral and the aluminum source or TiO2The mass ratio of (A) to (B) is 1: 10-3: 1;
s4, shaping and roasting: adding a proper amount of distilled water into the second mixed mineral obtained in the step S3, and uniformly stirring; then uniformly coating the sample separating sieve, putting the sample separating sieve into an oven, drying and taking out; knocking and separating the dried sample from the sample separating sieve to form particles; and then, the crucible is used for containing the catalyst and is placed into a muffle furnace for roasting, the roasting temperature is 400-800 ℃, the roasting time is 50-400 min, and the catalyst is taken out to prepare the catalyst.
2. The method of preparing a high efficiency rare earth tailings based SCR catalyst according to claim 1, wherein: in step S3, the aluminum source is aluminum nitrate or pseudo-boehmite.
3. The method of preparing a high efficiency rare earth tailings based SCR catalyst according to claim 1, wherein: in step S3, TiO is used2Mechanically stirring and mixing the first mineral mixture with adhesive, and adding TiO2。
4. The application of the catalyst is characterized in that: at NH3And NO is 1:1, with O2And N2Used for balancing, and the catalyst is used for removing flue gasA nitro catalyst.
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| CN112264034A (en) * | 2020-11-19 | 2021-01-26 | 安徽元琛环保科技股份有限公司 | Preparation method of low-temperature SCR denitration catalyst based on wolframite smelting slag |
| CN114588914A (en) * | 2022-03-21 | 2022-06-07 | 冯垚 | Method for preparing catalyst by using tailings |
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