CN112430098A - Self-protection silicon carbide corrosion-resistant material for water-cooled wall of pulverized coal gasification furnace - Google Patents
Self-protection silicon carbide corrosion-resistant material for water-cooled wall of pulverized coal gasification furnace Download PDFInfo
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
Abstract
The invention relates to a self-protection silicon carbide corrosion-resistant material for a water-cooled wall of a pulverized coal gasification furnace, which comprises the following raw materials in percentage by mass: 25-35% of 3-1mm acid-washing silicon carbide, 25-35% of 1mm-180 mesh acid-washing silicon carbide, 5-10% of 180-mesh acid-washing silicon carbide, 0-10% of 200-mesh acid-washing silicon carbide, 0-10% of acid-washing silicon carbide below 3000 meshes, 3-20% of alumina micro powder, 3-20% of a bonding agent, 1-15% of a phosphoric acid solution and 1-10% of magnesia. The self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier provided by the invention has excellent mechanical properties, thermal shock resistance, slag corrosion resistance and the like, and has great significance for improving the system operation efficiency, reducing the production cost and saving resources and energy.
Description
Technical Field
The invention relates to a self-protection silicon carbide corrosion-resistant material for a water-cooled wall of a pulverized coal gasification furnace, belonging to the technical field of high-temperature refractory materials.
Background
The coal chemical industry is an important way for clean and high-efficiency utilization of coal, and mainly converts carbon-containing raw materials into CO and H through a high-temperature and high-pressure chemical reaction process2And the like to obtain important chemical raw materials. The core of the gasification process is a gasification furnace which generates chemical reaction under high temperature and high pressure. The gasifier with the water-cooled wall structure is widely applied due to low investment, long service life, low maintenance cost and the like. The pulverized coal reacts with water at high temperature and high pressure in the gasification furnace, and part of the pulverized coal forms CO and H2And the other part forms ash to become slag. The furnace is in a strong reducing atmosphere, meanwhile, the slag is directly adhered to the surface of the water-cooled wall refractory lining, and the permeability of the slag is enhanced along with the reaction, so that the lining material is washed and abraded. When the thermal load of the water-cooled wall surface is high, the lining material of the water-cooled wall surface is required to have good thermal shock resistance so as to resist the cracking and peeling of the material caused by rapid temperature change or uneven heating; it is necessary and difficult to develop a material having good thermal shock resistance and good resistance to erosion by coal slag in a reducing atmosphere.
At present, although silicon carbide is used as a corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier, Al is used for the Tibetan plain, Chenyang and the like of the eastern electric oriental boiler2O3-SiO2-SiC composite material in which Fe needs to be controlled2O3And the content of SiC, but the problem of unstable coke hanging occurs in practical use, and the service life of the material is influenced. The Zhongtao and Yingsheng branches of Shanghai Tao refractory refer to SiC-Al2O3-Cr2O3The ramming material is prepared by silicon carbide, corundum, chrome corundum, ultrafine powder, aluminum-chromium phosphate binding agent and additive under specific conditions;the materials of the system do not refer to specific material proportion, preparation conditions and the like, and the materials contain Cr2O3And the material cost is high, and meanwhile, Cr is changed from +3 price to +6 price to pollute the environment in the using process. The development of a long-life heat-resistant corrosion-resistant material for the water-cooled wall of the pulverized coal gasification furnace, which has high heat conduction and self protection and is environment-friendly, is imperative.
Disclosure of Invention
The embodiment of the invention provides a self-protection silicon carbide corrosion-resistant material for a water-cooled wall of a pulverized coal gasification furnace. The self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier provided by the invention has excellent mechanical property, thermal shock resistance, slag corrosion resistance and other properties, can be quickly coked to form a self-protection layer due to good heat conduction property in actual use, can solve the problems that a pipeline of the water-cooled wall of the gasifier is easy to corrode, erode and wear in a strong reducing atmosphere and the like, and has great significance for improving the operation efficiency of a system, reducing the production cost and saving resources and energy.
The embodiment of the invention provides a self-protection silicon carbide corrosion-resistant material for a water-cooled wall of a pulverized coal gasification furnace, which comprises the following raw materials in percentage by mass:
some embodiments of the invention comprise the following raw materials in mass content:
according to some embodiments of the invention, the bonding agent is a PA inorganic adhesive, and the PA inorganic adhesive is prepared from H with a molar ratio of 3-4: 13PO4And Al (OH)3And (4) preparing.
In some embodiments of the present invention, the first and second electrodes are,the SiC content in the acid-washed silicon carbide is more than or equal to 99 percent; al in the alumina micro powder2O3The content is more than or equal to 99.99 percent; the MgO content in the magnesite is more than or equal to 97 percent.
In some embodiments of the invention, the additive is a mixed acidic material that promotes sintering of the material at elevated temperatures. The additive is preferably selected from one or more of sodium hexametaphosphate, polycyclic aromatic hydrocarbon sulfonate formaldehyde polymer and sodium dihydrogen phosphate.
In some embodiments of the invention, the admixture is a mixture of sodium hexametaphosphate and sodium dihydrogen phosphate.
Some embodiments of the invention comprise the following raw materials in mass content:
according to the invention, the self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier prepared by adopting the scheme of the raw materials and the dosage has good heat conduction performance when in actual use, and simultaneously reacts with ash at high temperature to form a self-protection layer on the surface of the material, so that the problems that the pipeline of the water-cooled wall of the gasifier is easy to corrode, erode and wear in strong reducing atmosphere and the like are solved better.
The embodiment of the invention also provides a preparation method of the self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasification furnace, which comprises the following steps:
step 1), mixing the acid-washed silicon carbide particles, the acid-washed silicon carbide powder, the alumina micropowder, the phosphoric acid solution, the magnesia and the admixture, adding 1/3-2/3 of a bonding agent, stirring, and sealing and ageing to obtain a premix;
and 2) adding the rest of the bonding agent into the premix material, stirring and molding.
In some embodiments of the invention, in the step 1), the stirring time is 2-8 min; the time for sealing and ageing is 20-28 h.
According to some preferred embodiments of the invention, the materials are prepared by accurately weighing the required raw materials and additives, pouring the raw materials and the additives into a stirrer, uniformly stirring, adding half of the amount of the bonding agent, stirring for 3-6 min, uniformly mixing the materials, and sealing for 24 h. And then adding the rest of the bonding agent into the material, stirring the pug into a construction state, forming, demolding, firing and the like in a specific mold, and further detecting the strength, the thermal shock resistance, the static crucible slag corrosion resistance and the like of the material.
According to the invention, the acid-washed silicon carbide is utilized to remove impurities such as metallic iron, iron oxide, magnesium, aluminum and the like in the silicon carbide, and the acid-washed silicon carbide is reacted with the alumina micro powder and the bonding agent to prepare a product which meets the requirements and has more excellent performances in all aspects. Furthermore, the inventor finds that the thermal shock resistance and slag corrosion resistance of the material can be improved by adopting the grading and using amount of acid-washing silicon carbide, and the mechanical strength of the material can be greatly improved by matching with the alumina micro powder, so that the material is durable. The self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasification furnace prepared by adopting the raw materials and the dosage has the characteristics of excellent mechanical strength, thermal shock resistance, slag corrosion resistance, service life and the like.
The invention has the beneficial effects that: the silicon carbide corrosion-resistant material provided by the invention has excellent mechanical property, thermal shock resistance, slag corrosion resistance and other properties; when the high-heat-conductivity material containing silicon carbide is adopted in the water-cooled wall type gasification furnace body, the surface of the material is quickly coked to form a protective layer when the water-cooled wall type gasification furnace body runs, the service life of the material is prolonged by adopting a coke furnace protection principle, and the long-period stable running of equipment is ensured; the silicon carbide corrosion-resistant material can solve the problems that a water-cooled wall pipeline of a gasification furnace is easy to corrode and erode and wear in a strong reducing atmosphere, improves the heat utilization rate of a device and the like, and has great significance for improving the operation efficiency of a system, reducing the production cost and saving resources and energy
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the present invention, the instruments and the like used are conventional products which are purchased from regular vendors, not indicated by manufacturers. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the following examples of the invention, acid-washing silicon carbide is treatment with sulfuric acid prior to use; the binding agent is industrial pure H3PO4And Al (OH)3Prepared of (H)3PO4And Al (OH)3In particular in a molar ratio of 3.5: 1. The additive is a mixture of sodium hexametaphosphate and sodium dihydrogen phosphate, and the mass ratio of the sodium hexametaphosphate to the sodium dihydrogen phosphate is 1: 1. The phosphoric acid solution is a technical grade phosphoric acid solution with the concentration of 85 percent. The SiC content is more than or equal to 99 percent. In the fine alumina powder, Al2O3The content is more than or equal to 99.99 percent. In the magnesite, the content of MgO is more than or equal to 97 percent.
The method for measuring the slag corrosion resistance of the refractory material in the embodiment of the invention comprises the following steps: the refractory material is made into a crucible blank, then ash slag is filled into the crucible, the erosion condition is measured under the condition of 1450 ℃ multiplied by 5h, and the condition that the material is good if the material is almost not eroded is judged.
Example 1
The embodiment provides a self-protection silicon carbide corrosion-resistant material for a water-cooled wall of a pulverized coal gasification furnace, which specifically comprises the following components: 30 percent of acid-washed silicon carbide with the grain size of 3-1mm, 25 percent of acid-washed silicon carbide with the grain size of 1mm-180 meshes, 8 percent of acid-washed silicon carbide with the grain size of 180 meshes, 5 percent of acid-washed silicon carbide with the grain size of 200 meshes, 5 percent of acid-washed silicon carbide with the grain size of less than 3000 meshes, 8 percent of alumina micro powder with the grain size of less than 5 mu m, 3 percent of magnesia with the grain size of 0.5-0mm, 8 percent of industrial-grade phosphoric acid solution and 0.25 percent of admixture are poured into a stirrer to be uniformly stirred, 4 percent of PA glue is added to be stirred for 3-6 min, and after the materials are uniformly mixed. The remaining 3.75% of the PA gum was then added to the material and the paste was stirred to a plastic state, rammed in a mold and then demolded. And (3) carrying out the following detection on the demolded material, wherein the detection comprises the material strength, thermal shock resistance, static crucible slag corrosion resistance and the like.
Table 1 example 1 test results
| Test items | Drying at 110 ℃ for 24h | After being burned at 1100 ℃ for 3h |
| Bulk density (g.cm)-3) | 2.61 | 2.58 |
| Normal temperature rupture strength (MPa) | 14.6 | 16.3 |
| Normal temperature compressive strength (MPa) | 82.8 | 106.7 |
| Rate of change of line after baking (%) | -- | -0.3 |
| Resistance to erosion | -- | Good (1450 ℃ x 5h) |
| Coefficient of thermal conductivityW/(m·K) | -- | 7.12(1000℃) |
| Thermal shock times (1100 ℃ water cooling) | -- | 36 |
Example 2
The embodiment provides a self-protection silicon carbide corrosion-resistant material for a water-cooled wall of a pulverized coal gasification furnace, which specifically comprises the following components: 25 percent of acid-washed silicon carbide with the grain size of 3-1mm, 30 percent of acid-washed silicon carbide with the grain size of 1mm-180 meshes, 8 percent of acid-washed silicon carbide with the grain size of 180 meshes, 5 percent of acid-washed silicon carbide with the grain size of 200 meshes, 5 percent of acid-washed silicon carbide with the grain size of less than 3000 meshes, 8 percent of alumina micro powder with the grain size of less than 5 mu m, 3 percent of magnesia with the grain size of 0.5-0mm, 8 percent of industrial-grade phosphoric acid solution and 0.25 percent of admixture are poured into a stirrer to be uniformly stirred, 4 percent of PA glue is added to be stirred for 3-6 min, and after the materials are uniformly mixed. The remaining 3.75% of the PA gum was then added to the material and the slurry was stirred into a plastic state, rammed into a mold and then demolded.
Table 2 example 2 test results
Example 3
The embodiment provides a self-protection silicon carbide corrosion-resistant material for a water-cooled wall of a pulverized coal gasification furnace, which specifically comprises the following components: 30 percent of acid-washed silicon carbide with the grain size of 3-1mm, 30 percent of acid-washed silicon carbide with the grain size of 1mm-180 meshes, 6 percent of acid-washed silicon carbide with the grain size of 180 meshes, 3 percent of acid-washed silicon carbide with the grain size of 200 meshes, 4 percent of acid-washed silicon carbide with the grain size of below 3000 meshes, 8 percent of alumina micro powder with the grain size of less than 5 mu m, 3 percent of magnesia with the grain size of 0.5-0mm, 8 percent of industrial-grade phosphoric acid solution and 0.25 percent of admixture are poured into a stirrer to be uniformly stirred, 4 percent of PA glue is added to be stirred for 3-6 min, and after the materials are uniformly mixed, the. The remaining 3.75% of the PA gum was then added to the material and the slurry was stirred into a plastic state, rammed into a mold and then demolded.
Table 3 example 3 test results
| Test items | Drying at 110 ℃ for 24h | After being burned at 1100 ℃ for 3h |
| Bulk density (g.cm)-3) | 2.60 | 2.58 |
| Normal temperature rupture strength (MPa) | 14.1 | 15.7 |
| Normal temperature compressive strength (MPa) | 84.8 | 98.1 |
| Rate of change of line after baking (%) | -- | -0.3 |
| Resistance to erosion | -- | Good effect(1450℃×5h) |
| Thermal conductivity W/(m.K) | 7.04(1000℃) | |
| Thermal shock times (1100 ℃ water cooling) | -- | 34 |
The self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasification furnace prepared according to the proportion in the embodiment has the characteristics of good mechanical strength, thermal shock resistance, slag corrosion resistance, service life and the like.
Experimental example 1
The product produced by the formula in the embodiment 1 is tried on the water-cooled wall of the gasification furnace, and the material in the embodiment forms a thicker coke layer when in use, has a self-protection effect and is good in use; the method is tried on 3 gasifier water-cooled walls designed in an XXXELECTRO Xboiler plant from 7 months in 2019 to the present (10 months in 2020), and the using effect is good.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasification furnace is characterized by comprising the following raw materials in mass content:
2. the self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier according to claim 1, which is characterized by comprising the following raw materials in mass content:
3. the self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier as claimed in claim 2, wherein the binder is PA inorganic adhesive.
4. The self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier according to claim 3, wherein the PA inorganic adhesive is prepared from H with a molar ratio of 3-4: 13PO4And Al (OH)3And (4) preparing.
5. The self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier according to claim 2, wherein the SiC content in the acid-washed silicon carbide is more than or equal to 99%; al in the alumina micro powder2O3The content is more than or equal to 99.99 percent; the MgO content in the magnesite is more than or equal to 97 percent.
6. The self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier as claimed in claim 2, wherein the additive is one or more selected from sodium hexametaphosphate, polycyclic aromatic hydrocarbon sulfonate formaldehyde polymer and sodium dihydrogen phosphate.
7. The method for preparing the self-protecting silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier in claim 6, wherein the additive is a mixture of sodium hexametaphosphate and sodium dihydrogen phosphate.
8. The method for preparing the self-protecting silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier as claimed in any one of claims 1 to 7,
9. the preparation method of the self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier according to any one of claims 1 to 8, which is characterized by comprising the following steps:
step 1), mixing the acid-washed silicon carbide particles, the acid-washed silicon carbide powder, the alumina micropowder, the phosphoric acid solution, the magnesia and the admixture, adding 1/3-2/3 of a bonding agent, stirring, and sealing and ageing to obtain a premix;
and 2) adding the rest of the bonding agent into the premix material, stirring and molding.
10. The preparation method of the self-protection silicon carbide corrosion-resistant material for the water-cooled wall of the pulverized coal gasifier according to claim 9, wherein in the step 1), the stirring time is 2-8 min; the time for sealing and ageing is 20-28 h.
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| CN113387706A (en) * | 2021-04-22 | 2021-09-14 | 北京金隅通达耐火技术有限公司 | Wear-resistant corrosion-resistant silicon carbide cap for waste heat boiler water-cooling wall lining |
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