CN1237142C - Method for preparing ceramic material grinding agent - Google Patents
Method for preparing ceramic material grinding agent Download PDFInfo
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- CN1237142C CN1237142C CN 200310105884 CN200310105884A CN1237142C CN 1237142 C CN1237142 C CN 1237142C CN 200310105884 CN200310105884 CN 200310105884 CN 200310105884 A CN200310105884 A CN 200310105884A CN 1237142 C CN1237142 C CN 1237142C
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Abstract
The present invention relates to a method for preparing a grinding agent for ceramic materials. Under 40 DEG C to 95 DEG C, 0.02 mol/L to 0.07 mol/L ammonium ceric nitrate solution and 5 to 10% acrylic acid solution by mass percentage are dipped into 10 to 20% maleic anhydride solution by mass percentage and are dipped and stirred simultaneously, the concentration of the ammonium ceric nitrate in the reaction solution is controlled within 0.5 mol/L to 2 m mol/L, and the molar ratio of the maleic anhydride solution to the acrylic acid solution is controlled within 1.7: 1 to 1: 3.1. The reaction solution reacts for 3.5 hours to 4.5 hours by stirring at a constant temperature, a pH value is regulated to 8 to 9 by a sodium hydroxide solution, the mixed solution is stirred uniformly, and 5 to 15% hydroquinone solution by mass percentage is dipped in the mixed solution.
Description
Technical field
The present invention relates to a kind of abradant auxiliary agent, particularly a kind of preparation method of stupalith grinding aid.
Background technology
The pulverizing of raw material is particularly requisite operation in the Production of Ceramics process of inorganic materials, and pulverize is the operation process of a high energy consumption, poor efficiency, in order to improve the efficient of grinding, adding an amount of grinding aid in process of lapping is a kind of simple effective method, grinding aid is meant in crushing process and adds on a small quantity, can significantly improve the chemical substance of crush efficiency.At present, mainly concentrate on processing two aspects of non-ferrous metal ore aspect and cement clinker, the application in the processing of ceramic industry raw material and study rarely found report about the research of grinding aid.Yet there are not special exploitation or research to be applicable to the grinding aid of most of ceramic raw materials, present application mainly still has the inorganic or organic additive of diminishing and suspension effect with some, it also has certain grinding-aid effect when having diminishing or suspension slip, for example Sodium hexametaphosphate 99, yellow soda ash and tripoly phosphate sodium STPP etc.In addition, also have some surfactant materials also can use, as alkoxide, amine salt, Sodium dodecylbenzene sulfonate, sulfonated lignin, Trisodium Citrate, oleic acid etc. as grinding aid.Grinding aid research at present mainly is to concentrate in existing inorganic salt or the grinding aid effect and mechanism of organic active agent to certain mineral, adopt Sodium hexametaphosphate 99, yellow soda ash as Guo Jianbin, find that it can improve the ultra-fine grinding efficiency [Guo Jianbin of zirconium silicate, Sodium hexametaphosphate 99, yellow soda ash improve the ultra-fine grinding efficiency research of zirconium silicate, nonmetalliferous ore, 2001,24 (2): 35-36]; Employing sodium humate such as Gao Sen and tripoly phosphate sodium STPP mix use, find can reduce when the thin blank of domestic ceramics grinds milling time [Gao Sen, the employing grinding aid shortens the milling time of ball mill, Hebei pottery, 29 (2): 40]; Tang Linsheng etc. have prepared many ammoniums sodium phosphate, find that it has grinding-aid effect [the synthetic and grinding aid performance study of many ammoniums sodium phosphate] preferably to the Wingdale raw material; Bu Jinglong and Shen Yi have prepared a kind of Organic Grinding Aid, find that it has grinding-aid effect preferably to zircon sand, but it does not report concrete grinding aid material [Bu Jinglong, Shen Yi, High-Efficient Organic Grinding Aid, pottery, 2000,4:31-32]; In addition, Zhang Jian, Wu Jiqiu find mixing such as Sodium dodecylbenzene sulfonate and water glass and tripoly phosphate sodium STPP are used and can be had certain grinding-aid effect to the porcelain stone raw material.American Klimpel; With Richard R. invented a kind of can be to the Organic Grinding Aid of effect such as ore, pottery and pigment and colliery, it obtains to contain at least the organic acid of three hydroxyls and 1-2 carboxyl by the method for oxidation glucide, find that it can play grinding-aid effect [Klimpel to many solid matters, Hydroxy-carboxylic acid grinding aids, United States Patent 5799882, September 1,1998]; The flat J1-151955 of rich open patent of day has reported and has utilized the polymeric sodium salt of propionic acid one vinylformic acid methyl as grinding aid, dry type is pulverized natural limestone and is produced water-ground limestone, the add-on of its grinding aid is to 0.05%～0.5% of ore deposit total amount, adopt this method dry grinding, can be easy to and produce effectively the micro mist water-ground limestone.The above-mentioned most of results of use of these grinding aids are relatively poor, as Sodium hexametaphosphate 99, yellow soda ash, Trisodium Citrate, tripoly phosphate sodium STPP etc.; And have can only be confined to a kind of ceramic raw material, only Wingdale is played effect as the polymeric sodium salt of propionic acid one vinylformic acid methyl, the grinding aid that has such as Sodium dodecylbenzene sulfonate and oleic acid etc. can produce a large amount of bubbles after being used in ceramic slurry, thereby should not use, even use also to such an extent that add a certain amount of defoamer again and be used, this will increase cost greatly.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of stupalith grinding aid, this grinding aid is added the mill efficiency that can significantly improve ceramic raw material in the ceramic raw material, reduce milling time, save energy consumption.
For achieving the above object, the technical solution used in the present invention is: at first maleic anhydride and vinylformic acid are dissolved in respectively that to be made into mass percent concentration in the distilled water be that 10～20% maleic anhydride and 5～10% acrylic acid solutions are standby; It is standby that the initiator ceric ammonium nitrate is dissolved in the ceric ammonium nitrate solution that is made into 0.02～0.07mol/L in the distilled water; Resorcinol is dissolved in distilled water is made into the Resorcinol solution for standby that concentration is mass percent concentration 5～15%; In reactor, be that 1.7: 1～1: 3.1 ratio is added drop-wise to acrylic acid solution in the maleic anhydride solution according to maleic anhydride and acrylic acid mol ratio with 40～95 ℃, in this process, simultaneously the initiator ceric ammonium nitrate solution is added drop-wise in the maleic anhydride solution, the concentration of ceric ammonium nitrate is 0.5～2.0mmol/L in the control reaction solution, stir while dripping, stirring reaction finishes reaction and obtains reaction solution after 3.5～4.5 hours under constant temperature; Adding sodium hydroxide solution in reaction solution, to make the pH value of reaction solution be 8～9, after stirring, drips a small amount of 1～2 Resorcinol solution and get final product.
The mass percent concentration of the said maleic anhydride of the present invention is 12～18%; Acrylic acid mass percent concentration is 6～9%; The concentration of initiator ceric ammonium nitrate solution is 0.04～0.06mol/L; The mass percent concentration 8～12% of Resorcinol solution; Under 50～85 ℃, be that 1.5: 1.3～1.2: 2.8 ratio is added drop-wise to acrylic acid solution in the maleic anhydride solution according to maleic anhydride and acrylic acid mol ratio, in this process, simultaneously the initiator ceric ammonium nitrate solution is added drop-wise in the maleic anhydride solution, the concentration of ceric ammonium nitrate is 0.8～1.5mmol/L in the control reaction solution, stir while dripping, stirring reaction finishes reaction and obtains reaction solution after 3.8～4.2 hours under constant temperature.
The present invention is a raw material with maleic anhydride, vinylformic acid, synthesized a kind of ceramic raw material grinding aid---the sodium salt of copolymer of maleic anhydride and acrylic acid, the result shows: it has grinding-aid effect to most of hard raw mineral materialss of being adopted in the ceramic industry such as zircon, quartz, feldspar, talcum etc.; It reduces milling time, the saving energy consumption with the mill efficiency that a spot of adding 0.01%-3.0% promptly can significantly improve ceramic raw material; Its result of use obviously is better than traditional ceramic grinding auxiliary agent such as yellow soda ash, water glass, tripoly phosphate sodium STPP etc.; Because the cost of the sodium salt of synthetic MA-AA multipolymer is lower, the product solid content is less, so its practical cost is lower simultaneously.
Embodiment
Embodiment 1: be that to be added drop-wise to mass percent concentration jointly be in 15% the maleic anhydride solution for 5% acrylic acid solution with 65 ℃ with the ceric ammonium nitrate solution of 0.05mol/L and mass percent concentration in reactor, stir while dripping, the concentration of ceric ammonium nitrate is 1.6mmol/L in the control reaction solution, the mol ratio of control maleic anhydride solution and acrylic acid solution is 1: 1, stirring reaction finishes reaction after 4 hours under constant temperature, with sodium hydroxide solution adjust pH 8, stir, the mass percent concentration that drips 1 is that 10% Resorcinol solution promptly obtains product.
The said products solution is calculated according to 100% purity, join in the planetary speed muller with different add-ons respectively and grinding together such as zircon, quartz and talcum, to investigate its grinding-aid effect to other ceramic raw material.Adopting the alumina-ceramic jar in the test is grinding pot (diameter 170mm), ballstone is ball-aluminium oxide ballstone (diameter 10mm), control pellet water ratio is material: ball: water=1: 2: 1,200 rev/mins of rotating speeds, grind and sieve with 200 mesh sieves after 5 minutes, with tailing over after the ten thousand/electronic balance weighing oven dry, with the quality that tails over what as the index of measurement grinding effect quality.Sample in the test when not adding grinding aid under the same terms is a check sample, uses as a comparison.
Grinding aid was to quartzy, zircon and steatitic grinding effect when table 1 was respectively different grinding aid add-on.
Sintetics and industrial grinding aid were to the grinding-aid effect comparison sheet of quartz when table 2 was different promoter addition
As can be seen from the table, add after the synthetic grinding aid 1%, in identical time range, 200 mesh screen residues of ball milling quartz are reduced to 1.71% by 7.17%, zircon is reduced to 3.24% by 9.39%, and talcum is reduced to 2.24% by 8.37%, illustrates that it has tangible grinding-aid effect.Compare with grinding aid water glass, yellow soda ash and tripoly phosphate sodium STPP etc. that traditional ceramic industry is commonly used, effect is very remarkable.
Table 1 sintetics is to quartz, zircon and steatitic grinding-aid effect table
| Grinding aid add-on (Wt%) | 0 | 0.01 | 0.1 | 1 | 3 | 5 | 10 | |
| Quartzy | 200 mesh screen residues | 7.17 | 2.82 | 1.97 | 1.71 | 2.66 | 3.15 | 3.24 |
| Zircon | 200 mesh screen residues | 9.39 | 6.58 | 3.37 | 3.24 | 3.67 | 4.59 | 5.57 |
| Talcum | 200 mesh screen residues | 8.37 | 3.59 | 2.52 | 2.24 | 3.05 | 3.68 | 4.12 |
Table 2 sintetics and industrial grinding aid are to the grinding-aid effect comparison sheet of quartz
| The grinding aid kind | Grinding aid add-on (Wt%) | 0 | 0.01 | 0.1 | 1 | 3 | 5 | 10 |
| Grinding aid | 200 mesh screen residues | 7.17 | 2.82 | 1.97 | 1.71 | 2.66 | 3.15 | 3.24 |
| Water glass | 200 mesh screen residues | 7.17 | 7.15 | 6.78 | 6.75 | 7.28 | 7.39 | 7.52 |
| Yellow soda ash | 200 mesh screen residues | 7.17 | 7.11 | 6.49 | 6.44 | 6.9 | 7.09 | 7.21 |
| Tripoly phosphate sodium STPP | 200 mesh screen residues | 7.17 | 6.98 | 6.37 | 6.24 | 6.67 | 6.78 | 6.82 |
Embodiment 2: be that 0.02mol/L ceric ammonium nitrate solution and mass percent concentration are that to be added drop-wise to mass percent concentration jointly be in 10% the maleic anhydride solution for 8% acrylic acid solution with 95 ℃ with concentration in reactor, stir while dripping, the concentration of ceric ammonium nitrate is 0.5mmol/L in the control reaction solution, the mol ratio of control maleic anhydride solution and acrylic acid solution is 1.7: 3.1, stirring reaction finishes reaction after 3.5 hours under constant temperature, with sodium hydroxide solution adjust pH 9, stir, drip 2 mass percent concentrations and be 5% Resorcinol solution and promptly obtain product.
The grinding aid test details of product is identical with embodiment 1.
Grinding aid was to quartzy and felspathic grinding effect when table 3 was respectively different grinding aid add-on.As can be seen, the synthetic grinding aid has tangible grinding-aid effect to feldspar and quartz in the table.
Table 3 sintetics is to quartzy and felspathic grinding-aid effect table
| Grinding aid add-on (%) | 0 | 0.01 | 0.1 | 1 | 3 | 5 | 10 | |
| Quartzy | 200 mesh screen residues | 7.17 | 3.00 | 2.75 | 2.72 | 2.84 | 3.22 | 3.58 |
| Feldspar | 200 mesh screen residues | 6.98 | 4.35 | 4.46 | 2.03 | 2.69 | 3.56 | 3.64 |
Embodiment 3: be that the ceric ammonium nitrate solution of 0.07mol/L and mass percent concentration are that to be added drop-wise to mass percent concentration jointly be in 20% the maleic anhydride solution for 10% acrylic acid solution with 40 ℃ with concentration in reactor, stir while dripping, the concentration of ceric ammonium nitrate is for being 2mmol/L in the control reaction solution, the mol ratio of control maleic anhydride solution and acrylic acid solution is 1.5: 2, stirring reaction finishes reaction after 4 hours under constant temperature, with sodium hydroxide solution adjust pH 8.5, stir, drip 1 mass percent concentration and be 15% Resorcinol solution and promptly obtain product.
The grinding aid test details of product is identical with embodiment 1.
Grinding aid was to quartzy and felspathic grinding effect when table 4 was respectively different grinding aid add-on.The synthetic grinding aid has tangible grinding-aid effect to the domestic ceramics batching that typically contains clay simultaneously.
Table 4 sintetics is to the grinding-aid effect table of quartzy and feldspar and typical domestic ceramics blank proportioning
| Grinding aid add-on (%) | 0 | 0.01 | 0.1 | 1 | 3 | 5 | 10 | |
| Quartzy | 200 mesh screen residues | 7.17 | 3.53 | 3.25 | 2.88 | 2.71 | 2.99 | 4.81 |
| Feldspar | 200 mesh screen residues | 6.98 | 3.35 | 3.16 | 2.83 | 2.62 | 3.24 | 4.67 |
| Domestic ceramics blank (quartz: feldspar: Hongjiang soil Wt%=30: 30: 40) | 200 mesh screen residues | 6.76 | 2.95 | 2.78 | 1.68 | 1.73 | 2.38 | 5.23 |
Claims (9)
1, a kind of preparation method of stupalith grinding aid is characterized in that:
1) at first maleic anhydride and vinylformic acid are dissolved in respectively that to be made into mass percent concentration in the distilled water be that 10～20% maleic anhydride and 5～10% acrylic acid solutions are standby;
2) it is standby the initiator ceric ammonium nitrate to be dissolved in the ceric ammonium nitrate solution that is made into 0.02～0.07mol/L in the distilled water;
3) Resorcinol is dissolved in distilled water and is made into the Resorcinol solution for standby that concentration is mass percent concentration 5～15%;
4) in reactor, be that 1.7: 1～1: 3.1 ratio is added drop-wise to acrylic acid solution in the maleic anhydride solution according to maleic anhydride and acrylic acid mol ratio with 40～95 ℃, in this process, simultaneously the initiator ceric ammonium nitrate solution is added drop-wise in the maleic anhydride solution, the concentration of ceric ammonium nitrate is 0.5～2.0mmol/L in the control reaction solution, stir while dripping, stirring reaction finishes reaction and obtains reaction solution after 3.5～4.5 hours under constant temperature;
5) adding sodium hydroxide solution in reaction solution, to make the pH value of reaction solution be 8～9, after stirring, drips a small amount of 1～2 Resorcinol solution and get final product.
2, the preparation method of stupalith grinding aid according to claim 1 is characterized in that: the mass percent concentration of said maleic anhydride is 12～18%.
3, the preparation method of stupalith grinding aid according to claim 1 is characterized in that: said acrylic acid mass percent concentration is 6～9%.
4, the preparation method of stupalith grinding aid according to claim 1 is characterized in that: the concentration of said initiator ceric ammonium nitrate solution is 0.04～0.06mol/L.
5, the preparation method of stupalith grinding aid according to claim 1 is characterized in that: the mass percent concentration 8～12% of said Resorcinol solution.
6, the preparation method of stupalith grinding aid according to claim 1, it is characterized in that: said is that 1.5: 1.3～1.2: 2.8 ratio is added drop-wise to acrylic acid solution in the maleic anhydride solution according to maleic anhydride and acrylic acid mol ratio under 50～85 ℃, in this process, simultaneously the initiator ceric ammonium nitrate solution is added drop-wise in the maleic anhydride solution, the concentration of ceric ammonium nitrate is 0.8～1.5mmol/L in the control reaction solution, stir while dripping, stirring reaction finishes reaction and obtains reaction solution after 3.8～4.2 hours under constant temperature.
7, the preparation method of stupalith grinding aid according to claim 1, it is characterized in that: under 65 ℃ be that to be added drop-wise to mass percent concentration jointly be in 15% the maleic anhydride solution for 5% acrylic acid solution the ceric ammonium nitrate solution of 0.05mol/L and mass percent concentration, stir while dripping, the concentration of ceric ammonium nitrate is 1.6mmol/L in the control reaction solution, the mol ratio of control maleic anhydride solution and acrylic acid solution is 1: 1, stirring reaction finishes reaction after 4 hours under constant temperature, with sodium hydroxide solution adjust pH 8, stir, the mass percent concentration that drips 1 is that 10% Resorcinol solution gets final product.
8, the preparation method of stupalith grinding aid according to claim 1, it is characterized in that: under 95 ℃ be that 0.02mol/L ceric ammonium nitrate solution and mass percent concentration are that to be added drop-wise to mass percent concentration jointly be in 10% the maleic anhydride solution for 8% acrylic acid solution concentration, stir while dripping, the concentration of ceric ammonium nitrate is 0.5mmol/L in the control reaction solution, the mol ratio of control maleic anhydride solution and acrylic acid solution is 1.7: 3.1, stirring reaction finishes reaction after 3.5 hours under constant temperature, with sodium hydroxide solution adjust pH 9, stir, drip 2 mass percent concentrations and be 5% Resorcinol solution and get final product.
9, the preparation method of stupalith grinding aid according to claim 1, it is characterized in that: under 40 ℃ be that the ceric ammonium nitrate solution of 0.07mol/L and mass percent concentration are that to be added drop-wise to mass percent concentration jointly be in 20% the maleic anhydride solution for 10% acrylic acid solution concentration, stir while dripping, the concentration of ceric ammonium nitrate is for being 2mmol/L in the control reaction solution, the mol ratio of control maleic anhydride solution and acrylic acid solution is 1.5: 2, stirring reaction finishes reaction after 4 hours under constant temperature, with sodium hydroxide solution adjust pH 8.5, stir, drip 1 mass percent concentration and be 15% Resorcinol solution and get final product.
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| CN 200310105884 CN1237142C (en) | 2003-11-05 | 2003-11-05 | Method for preparing ceramic material grinding agent |
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| CN 200310105884 CN1237142C (en) | 2003-11-05 | 2003-11-05 | Method for preparing ceramic material grinding agent |
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| CN114146808A (en) * | 2021-12-27 | 2022-03-08 | 湖南格林朗科技有限公司 | Efficient ceramic grinding aid and preparation method thereof |
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