CN108083780B - Filler ceramic ball and preparation method thereof - Google Patents
Filler ceramic ball and preparation method thereof Download PDFInfo
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- CN108083780B CN108083780B CN201711459341.5A CN201711459341A CN108083780B CN 108083780 B CN108083780 B CN 108083780B CN 201711459341 A CN201711459341 A CN 201711459341A CN 108083780 B CN108083780 B CN 108083780B
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- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
- C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
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- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
Abstract
The invention discloses a filler ceramic ball and a preparation method thereof, wherein the ceramic ball comprises the following raw materials in parts by weight: 80-90 parts of aluminum oxide, 3-5 parts of magnesium oxide, 2-3 parts of titanium oxide, 1-3 parts of zirconium oxide, 3-5 parts of kaolin, 1-5 parts of spodumene, 3-5 parts of vermiculite, 5-10 parts of gravel, 1-3 parts of volcanic rock and 5-8 parts of crab shell powder. The ceramic ball prepared by the method has the advantages of no crack, no bubble, low water absorption, high acid resistance and alkali resistance, large sudden change temperature difference resistance, large bulk density and high compressive strength, comprehensively improves the quality of the ceramic ball, better plays the role of a catalyst, and greatly improves the reaction speed and the reaction effect in the tower. In addition, the special processes of preparation, mixing, sintering and the like of the crab shell powder further improve the quality of the porcelain ball.
Description
Technical Field
The invention relates to the technical field of porcelain balls, in particular to a filler porcelain ball and a preparation method thereof.
Background
The ceramic ball is widely used in the industries of petroleum, chemical industry, chemical fertilizer, natural gas, environmental protection and the like, and is used as a covering and supporting material of a catalyst in a reactor and a tower filler. It has the features of high temperature and high pressure resistance, low water absorption and stable chemical performance. Can withstand corrosion by acids, bases and other organic solvents, and can withstand temperature changes that occur during production. The main function is to increase the distribution points of gas or liquid, support and protect the active catalyst with low strength. The porcelain balls can be classified into filler porcelain balls and grinding porcelain balls according to purposes. The stuffing ceramic ball widely used in petrochemical production reaction tower can cover and support various catalysts, and raise the reaction speed and effect in the tower. However, the quality of the existing filler porcelain ball is poor, and the function of the catalyst cannot be fully exerted.
Disclosure of Invention
In view of the above, the invention provides a filler ceramic ball and a preparation method thereof, which solve the technical problems.
The technical means adopted by the invention are as follows: the filler porcelain ball comprises the following raw materials in parts by weight: 80-90 parts of aluminum oxide, 3-5 parts of magnesium oxide, 2-3 parts of titanium oxide, 1-3 parts of zirconium oxide, 3-5 parts of kaolin, 1-5 parts of spodumene, 3-5 parts of vermiculite, 5-10 parts of gravel, 1-3 parts of volcanic rock and 5-8 parts of crab shell powder.
Further, the porcelain ball comprises the following raw materials in parts by weight: 85 parts of aluminum oxide, 4 parts of magnesium oxide, 2 parts of titanium oxide, 2 parts of zirconium oxide, 4 parts of kaolin, 3 parts of spodumene, 4 parts of vermiculite, 8 parts of gravel, 2 parts of volcanic rock and 7 parts of crab shell powder.
The invention also provides a preparation method of the filler porcelain ball, which comprises the following steps:
s1, preparing crab shell powder: taking crab shells, cleaning, soaking in a sodium chlorate solution, drying, crushing and pulverizing to obtain crab shell powder;
s2, mixing materials: putting alumina, spodumene, vermiculite, gravel and volcanic rock in a ball mill according to the weight ratio, carrying out primary ball milling for 4-6 h, putting the ball milled mixture into an alkaline solution with the concentration of 0.5-1 mol/L, treating for 1-2 h, and drying to obtain an alkali treated sample; adding kaolin, magnesium oxide, titanium oxide, zirconium oxide and crab shell powder to perform secondary ball milling for 8-12 hours to obtain a mixture;
s3, spray drying: spray drying the mixture obtained in the step S2, wherein the inlet temperature is 130-150 ℃, and the outlet temperature is 70-100 ℃, so as to obtain powder;
s4, molding: putting the powder obtained in the step S3 into a ball forming mill, continuously spraying water mist, rolling the powder into balls, wherein the water content of the balls is 9-12%;
s5, sintering: and (4) putting the material obtained in the step (S4) into a vacuum sintering furnace, heating to 850-1000 ℃ at a speed of 10-20 ℃/min, preserving heat for 3-5 h, heating to 1400-1600 ℃ at a speed of 25-35 ℃/min, preserving heat for 8-12 h, cooling to 100-300 ℃ at a speed of 30-40 ℃/min, and naturally cooling to normal temperature to obtain the material.
Further, in the step S1, the concentration of the sodium chlorate solution is 0.1 to 0.3mol/L, and the soaking time is 20 to 40 min.
Further, in the step S1, the mesh number of the crab shell powder is more than 200 meshes.
Further, in step S2, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.
Further, in the step S2, the first ball milling is performed until the particle size of the mixture is 0.9 to 1.1 μm, and the second ball milling is performed until the particle size of the mixture is 0.4 to 0.6 μm.
Further, in the step S3, the inlet temperature is 140 ℃.
Further, in step S4, the water content after balling is 10%.
Further, in the step S5, the temperature is increased to 900 ℃ at a speed of 15 ℃/min, and the temperature is kept for 4 h; heating to 1500 ℃ at the speed of 30 ℃/min, and then preserving heat for 10 h; then the temperature is reduced to 200 ℃ at 35 ℃/min, and then the mixture is naturally cooled to the normal temperature.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts vermiculite, gravel, volcanic rock and crab shell powder, combines alumina, magnesia, titania, zirconia, kaolin and spodumene, and has scientific proportioning, and the prepared ceramic ball has no crack and no bubble, low water absorption, high acid resistance and alkali resistance, large sudden change temperature resistance, large stacking density and large compressive strength, comprehensively improves the quality of the ceramic ball, fully plays the role of a catalyst, and greatly improves the reaction speed and the reaction effect in the tower. Moreover, the special processes of preparation, mixing, sintering and the like of the crab shell powder further improve the quality of the porcelain ball and are more beneficial to the exertion of the function of the catalyst.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
The filler porcelain ball comprises the following raw materials in parts by weight: 80 parts of aluminum oxide, 3 parts of magnesium oxide, 2 parts of titanium oxide, 1 part of zirconium oxide, 3 parts of kaolin, 1 part of spodumene, 3 parts of vermiculite, 5 parts of gravel, 1 part of volcanic rock and 5 parts of crab shell powder.
Example 2
The filler porcelain ball comprises the following raw materials in parts by weight: 90 parts of aluminum oxide, 5 parts of magnesium oxide, 3 parts of titanium oxide, 3 parts of zirconium oxide, 5 parts of kaolin, 5 parts of spodumene, 5 parts of vermiculite, 10 parts of gravel, 3 parts of volcanic rock and 8 parts of crab shell powder.
Example 3
The filler porcelain ball comprises the following raw materials in parts by weight: 85 parts of aluminum oxide, 4 parts of magnesium oxide, 2 parts of titanium oxide, 2 parts of zirconium oxide, 4 parts of kaolin, 3 parts of spodumene, 4 parts of vermiculite, 8 parts of gravel, 2 parts of volcanic rock and 7 parts of crab shell powder.
The preparation method of the filler ceramic ball of the embodiment 1 to 3 includes the following steps:
s1, preparing crab shell powder: taking crab shells, cleaning, soaking in 0.2mol/L sodium chlorate solution for 30min, drying, pulverizing into powder, and sieving with a 200-mesh sieve to obtain crab shell powder;
s2, mixing materials: putting alumina, spodumene, vermiculite, gravel and volcanic rock in a ball mill according to the weight ratio, carrying out first ball milling for 5 hours until the granularity of the mixture is 0.9-1.1 mu m, putting the mixture into a sodium hydroxide solution with the concentration of 0.8mol/L after ball milling, carrying out alkali treatment for 1.5 hours, and drying to obtain an alkali-treated sample; adding kaolin, magnesium oxide, titanium oxide, zirconium oxide and crab shell powder, and performing secondary ball milling for 10 hours until the granularity of the mixture is 0.4-0.6 mu m to obtain a mixture;
s3, spray drying: spray drying the mixture obtained in the step S2, wherein the inlet temperature is 140 ℃, and the outlet temperature is 80-90 ℃ to obtain powder;
s4, molding: putting the powder obtained in the step S3 into a ball forming mill, continuously spraying water mist, rolling the powder into balls, wherein the water content of the balls is 10%;
s5, sintering: putting the material obtained in the step S4 into a vacuum sintering furnace, heating to 900 ℃ at a speed of 15 ℃/min, and preserving heat for 4 h; heating to 1500 ℃ at the speed of 30 ℃/min, and then preserving heat for 10 h; cooling to 200 deg.C at 35 deg.C/min, and naturally cooling to normal temperature.
Example 4
The filler porcelain ball comprises the following raw materials in parts by weight: 85 parts of aluminum oxide, 4 parts of magnesium oxide, 2 parts of titanium oxide, 2 parts of zirconium oxide, 4 parts of kaolin, 3 parts of spodumene, 4 parts of vermiculite, 8 parts of gravel, 2 parts of volcanic rock and 7 parts of crab shell powder.
The preparation method of the filler porcelain ball comprises the following steps:
s1, preparing crab shell powder: taking crab shells, cleaning, soaking in 0.1mol/L sodium chlorate solution for 40min, drying, pulverizing into powder, and sieving with a 300-mesh sieve to obtain crab shell powder;
s2, mixing materials: putting alumina, spodumene, vermiculite, gravel and volcanic rock in a ball mill according to the weight ratio, carrying out first ball milling for 4 hours until the granularity of the mixture is 0.9-1.1 mu m, putting the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L after ball milling, carrying out alkali treatment for 2 hours, and drying to obtain an alkali-treated sample; adding kaolin, magnesium oxide, titanium oxide, zirconium oxide and crab shell powder, and performing secondary ball milling for 8 hours until the granularity of the mixture is 0.4-0.6 mu m to obtain a mixture;
s3, spray drying: spray drying the mixture obtained in the step S2, wherein the inlet temperature is 130 ℃, and the outlet temperature is 70-80 ℃, so as to obtain powder;
s4, molding: putting the powder obtained in the step S3 into a ball forming mill, continuously spraying water mist, rolling the powder into balls, wherein the water content of the balls is 9%;
s5, sintering: and (4) putting the material obtained in the step (S4) into a vacuum sintering furnace, heating to 850 ℃ at a speed of 10 ℃/min, preserving heat for 5h, heating to 1400 ℃ at a speed of 25 ℃/min, preserving heat for 12h, cooling to 300 ℃ at a speed of 30 ℃/min, and naturally cooling to normal temperature to obtain the material.
Example 5
The filler porcelain ball comprises the following raw materials in parts by weight: 85 parts of aluminum oxide, 4 parts of magnesium oxide, 2 parts of titanium oxide, 2 parts of zirconium oxide, 4 parts of kaolin, 3 parts of spodumene, 4 parts of vermiculite, 8 parts of gravel, 2 parts of volcanic rock and 7 parts of crab shell powder.
The preparation method of the filler porcelain ball comprises the following steps:
s1, preparing crab shell powder: taking crab shells, cleaning, soaking in 0.3mol/L sodium chlorate solution for 20min, drying, pulverizing into powder, and sieving with a 200-mesh sieve to obtain crab shell powder;
s2, mixing materials: putting alumina, spodumene, vermiculite, gravel and volcanic rock in a ball mill according to the weight ratio, carrying out first ball milling for 6 hours until the granularity of the mixture is 0.9-1.1 mu m, putting the mixture into a sodium hydroxide solution with the concentration of 1mol/L after ball milling, carrying out alkali treatment for 1 hour, and drying to obtain an alkali-treated sample; adding kaolin, magnesium oxide, titanium oxide, zirconium oxide and crab shell powder, and performing secondary ball milling for 12 hours until the granularity of the mixture is 0.4-0.6 mu m to obtain a mixture;
s3, spray drying: spray drying the mixture obtained in the step S2, wherein the inlet temperature is 150 ℃, and the outlet temperature is 90-100 ℃, so as to obtain powder;
s4, molding: putting the powder obtained in the step S3 into a ball forming mill, continuously spraying water mist, rolling the powder into balls, wherein the water content of the balls is 12%;
s5, sintering: and (5) putting the material obtained in the step (S4) into a vacuum sintering furnace, heating to 1000 ℃ at a speed of 20 ℃/min, preserving heat for 3h, heating to 1600 ℃ at a speed of 35 ℃/min, preserving heat for 8h, cooling to 100 ℃ at a speed of 40 ℃/min, and naturally cooling to normal temperature to obtain the material.
Example 6
The present embodiment is different from embodiment 3 in that, in step S1: the crab shell is not soaked in sodium chlorate solution and is directly dried.
Example 7
The present embodiment is different from embodiment 3 in that, in step S2: and directly carrying out secondary ball milling without alkali treatment after the primary ball milling.
Example 8
The present embodiment is different from embodiment 3 in that, in step S2: putting alumina, kaolin, magnesia, titanium oxide, zirconia and crab shell powder in a ball mill according to the weight ratio, carrying out first ball milling for 10 hours, putting the ball milled powder in a sodium hydroxide solution with the concentration of 0.8mol/L, carrying out alkali treatment for 1.5 hours, and drying to obtain an alkali treated sample; and adding spodumene, vermiculite, gravel and volcanic rock, and performing secondary ball milling for 5 hours to obtain a mixture.
Example 9
The present embodiment is different from embodiment 3 in that, in step S5: and (4) putting the material obtained in the step (S4) into a vacuum sintering furnace, heating to 900 ℃ at a speed of 30 ℃/min, preserving heat for 4h, heating to 1500 ℃ at a speed of 40 ℃/min, preserving heat for 10h, cooling to 200 ℃ at a speed of 20 ℃/min, and naturally cooling to normal temperature.
Comparative example 1
The filler porcelain ball comprises the following raw materials in parts by weight: 85 parts of alumina, 4 parts of magnesia, 2 parts of titanium oxide, 2 parts of zirconia, 4 parts of kaolin and 3 parts of spodumene.
The preparation method of the filler porcelain ball comprises the following steps:
s1, mixing materials: putting alumina and spodumene into a ball mill according to the weight ratio, carrying out first ball milling for 5 hours until the granularity of the mixture is 0.9-1.1 mu m, putting the mixture into a sodium hydroxide solution with the concentration of 0.8mol/L after ball milling, carrying out alkali treatment for 1.5 hours, and drying to obtain an alkali treated sample; adding kaolin, magnesium oxide, titanium oxide and zirconium oxide, and performing secondary ball milling for 10 hours until the granularity of the mixture is 0.4-0.6 mu m to obtain a mixture;
s2, spray drying: spray drying the mixture obtained in the step S1, wherein the inlet temperature is 140 ℃, and the outlet temperature is 80-90 ℃ to obtain powder;
s3, molding: putting the powder obtained in the step S2 into a ball forming mill, continuously spraying water mist, rolling the powder into balls, wherein the water content of the balls is 10%;
s4, sintering: putting the material obtained in the step S3 into a vacuum sintering furnace, heating to 900 ℃ at a speed of 15 ℃/min, and preserving heat for 4 h; heating to 1500 ℃ at the speed of 30 ℃/min, and then preserving heat for 10 h; cooling to 200 deg.C at 35 deg.C/min, and naturally cooling to normal temperature.
Comparative example 2
The filler porcelain ball comprises the following raw materials in parts by weight: 70 parts of aluminum oxide, 6 parts of magnesium oxide, 5 parts of titanium oxide, 5 parts of zirconium oxide, 6 parts of kaolin, 8 parts of spodumene, 8 parts of vermiculite, 3 parts of gravel, 5 parts of volcanic rock and 10 parts of crab shell powder. The preparation method is the same as in example 3.
The porcelain balls prepared in the embodiments 1-9 and the comparative examples 1-2 of the invention are subjected to performance tests, and the test results are as follows:
the results show that the ceramic ball prepared by the method has the advantages of no crack, no bubble, low water absorption, high acid resistance and alkali resistance, large sudden change temperature difference resistance, large bulk density and high compressive strength, and the quality of the ceramic ball is comprehensively improved. Wherein, the comparison of comparative examples 1-2 with example 3 shows that the invention adopts vermiculite, gravel, volcanic rock and crab shell powder, combines alumina, magnesia, titania, zirconia, kaolin and spodumene, has scientific proportioning, makes the porcelain ball have good performance, fully exerts the function of catalyst, and greatly improves the reaction speed and reaction effect in the tower. In addition, compared with the embodiment 3, the porcelain ball of the embodiment 3 has the best quality, which shows that the formula proportion of the embodiment 3 is the best; compared with the example 3, the ceramic balls in the example 3 have the best quality, which shows that the preparation method of the example 3 has the best technological parameters. Compared with the embodiment 3, the embodiment 6-9 has relatively best quality of the porcelain ball in the embodiment 3, and shows that the special processes of preparing, mixing, sintering and the like of the crab shell powder further improve the quality of the porcelain ball and are more beneficial to the exertion of the function of the catalyst.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the filler porcelain ball is characterized by comprising the following steps:
s1, preparing crab shell powder: taking crab shells, cleaning, soaking in a sodium chlorate solution, drying, crushing and pulverizing to obtain crab shell powder;
s2, mixing materials: taking 80-90 parts of alumina, 1-5 parts of spodumene, 3-5 parts of vermiculite, 5-10 parts of gravel and 1-3 parts of volcanic rock according to the weight ratio, placing the mixture into a ball mill for first ball milling for 4-6 hours, placing the mixture into an alkaline solution with the concentration of 0.5-1 mol/L after ball milling, treating the mixture for 1-2 hours, and drying the mixture to obtain an alkali-treated sample; then adding 3-5 parts of kaolin, 3-5 parts of magnesium oxide, 2-3 parts of titanium oxide, 1-3 parts of zirconium oxide and 5-8 parts of crab shell powder, and carrying out secondary ball milling for 8-12 hours to obtain a mixture;
s3, spray drying: spray drying the mixture obtained in the step S2, wherein the inlet temperature is 130-150 ℃, and the outlet temperature is 70-100 ℃, so as to obtain powder;
s4, molding: putting the powder obtained in the step S3 into a ball forming mill, continuously spraying water mist, rolling the powder into balls, wherein the water content of the balls is 9-12%;
s5, sintering: and (4) putting the material obtained in the step (S4) into a vacuum sintering furnace, heating to 850-1000 ℃ at a speed of 10-20 ℃/min, preserving heat for 3-5 h, heating to 1400-1600 ℃ at a speed of 25-35 ℃/min, preserving heat for 8-12 h, cooling to 100-300 ℃ at a speed of 30-40 ℃/min, and naturally cooling to normal temperature to obtain the material.
2. The preparation method of the filler porcelain ball according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 85 parts of aluminum oxide, 4 parts of magnesium oxide, 2 parts of titanium oxide, 2 parts of zirconium oxide, 4 parts of kaolin, 3 parts of spodumene, 4 parts of vermiculite, 8 parts of gravel, 2 parts of volcanic rock and 7 parts of crab shell powder.
3. The method for preparing porcelain ball with filler according to claim 1, wherein in step S1, the concentration of the sodium chlorate solution is 0.1-0.3 mol/L, and the soaking time is 20-40 min.
4. The method as claimed in claim 1 or 3, wherein the crab shell powder has a mesh size of 200 meshes or more in the step S1.
5. The method of claim 1, wherein in step S2, the alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
6. The method of claim 1, wherein in step S2, the first ball milling is performed until the particle size of the mixture is 0.9-1.1 μm, and the second ball milling is performed until the particle size of the mixture is 0.4-0.6 μm.
7. The method of claim 1, wherein the inlet temperature of step S3 is 140 ℃.
8. The method for preparing porcelain beads as filler according to claim 1, wherein the water content after the balling is 10% in step S4.
9. The method for preparing the ceramic ball as the filler according to claim 1, wherein in the step S5, the temperature is raised to 900 ℃ at a rate of 15 ℃/min, and the temperature is kept for 4 h; heating to 1500 ℃ at the speed of 30 ℃/min, and then preserving heat for 10 h; then the temperature is reduced to 200 ℃ at 35 ℃/min, and then the mixture is naturally cooled to the normal temperature.
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| CN1533999A (en) * | 2003-04-02 | 2004-10-06 | 珠海粤科清华电子陶瓷有限公司 | Low temperature sintered 99 aluminium oxide ceramic and its production method and use |
| UA80519C2 (en) * | 2007-03-13 | 2007-09-25 | Method for preparation of complex raw material composition for production of ceramics (variants) | |
| CN103242035A (en) * | 2013-05-15 | 2013-08-14 | 金刚新材料股份有限公司 | Method for improving appearance quality of inertial porcelain ball |
| CN103304221A (en) * | 2013-04-23 | 2013-09-18 | 金刚新材料股份有限公司 | Method for preparing inert porcelain ball by using aluminum oxide dust-recovery powder |
| CN103382096A (en) * | 2013-06-26 | 2013-11-06 | 蚌埠德美过滤技术有限公司 | Anti-microbial ceramic filter core and preparation method thereof |
| CN106478996A (en) * | 2016-09-13 | 2017-03-08 | 浙江大学 | A kind of method and its application for preparing calcium carbonate chitin composite granule with crab shell as raw material |
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| CN1533999A (en) * | 2003-04-02 | 2004-10-06 | 珠海粤科清华电子陶瓷有限公司 | Low temperature sintered 99 aluminium oxide ceramic and its production method and use |
| UA80519C2 (en) * | 2007-03-13 | 2007-09-25 | Method for preparation of complex raw material composition for production of ceramics (variants) | |
| CN103304221A (en) * | 2013-04-23 | 2013-09-18 | 金刚新材料股份有限公司 | Method for preparing inert porcelain ball by using aluminum oxide dust-recovery powder |
| CN103242035A (en) * | 2013-05-15 | 2013-08-14 | 金刚新材料股份有限公司 | Method for improving appearance quality of inertial porcelain ball |
| CN103382096A (en) * | 2013-06-26 | 2013-11-06 | 蚌埠德美过滤技术有限公司 | Anti-microbial ceramic filter core and preparation method thereof |
| CN106478996A (en) * | 2016-09-13 | 2017-03-08 | 浙江大学 | A kind of method and its application for preparing calcium carbonate chitin composite granule with crab shell as raw material |
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