CN111484058A - Method for co-producing low-sodium high-temperature alumina by using polyaluminium chloride - Google Patents
Method for co-producing low-sodium high-temperature alumina by using polyaluminium chloride Download PDFInfo
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Abstract
The invention discloses a method for coproducing low-sodium high-temperature alumina by using polyaluminium chloride, which comprises the following steps of mixing an aluminum hydroxide solution and a hydrochloric acid solution, and carrying out a dissolution reaction to obtain a polyaluminium chloride solution; mixing aluminum oxide with the polyaluminium chloride solution, and then carrying out dealkalization-polymerization reaction to obtain a mixed solution; filtering the mixed solution to obtain a filter cake and a filtrate; and roasting the filter cake to obtain low-sodium high-temperature alumina, and concentrating the filtrate to obtain the polyaluminium chloride. By adopting the method, the price of the preparation raw materials is low, the preparation process is environment-friendly, and not only the alumina with extremely low sodium content is obtained, but also the high-purity polyaluminium chloride is obtained, and the polyaluminium chloride can be used as a water purifying agent.
Description
Technical Field
The invention belongs to the field of light metal metallurgy, and particularly relates to a method for co-producing low-sodium high-temperature alumina by using polyaluminium chloride.
Background
Polyaluminium chloride (PAC) is an inorganic high-molecular coagulant between AlCl3And Al (OH)3The water-soluble inorganic high molecular polymer has high electric neutralization and bridging effects on colloids and particles in water. The synthesis method comprises a metallic aluminum method, an active aluminum hydroxide method, an aluminum oxide method, an aluminum chloride method, an alkali dissolution method and the like.
The low-sodium alumina is a white inorganic powder material, has the advantages of low Na content, narrow granularity dispersion, large specific surface area, high whiteness, low hardness, low refractive index, good compatibility with organic high-molecular materials and the like, and is mainly applied to polishing of metal, glass and various ceramic products and a sintering aid of non-oxide ceramics. Because the low-sodium alumina also has the characteristics of high melting point (2040 ℃), strong chemical sluggish, good electrical insulation, high hardness and good wear resistance, the low-sodium alumina can be widely applied to the fields of refractory materials, car spark plugs, electronic substrates, wear-resistant ceramics and the like, and has very wide application prospect.
Na2The O content is an important technical index of low-sodium alumina, Na2The content of O directly affects the compressive strength and electrical insulation of the alumina product. If Na2High content of O, high conductivity of alumina, poor wear resistance, high temperature calcination of Al2O3The conversion rate is low.
The domestic method for producing low-sodium high-temperature alumina generally comprises the following steps: a direct calcining method of high-purity aluminum raw materials; calcining process for removing sodium by acid washing of industrial grade aluminium raw material. Both of these methods have great disadvantages, the former is 10 times as high as industrial alumina because of expensive high-purity aluminum raw material and high cost, and the latter needs to use acid and alkali reaction to remove sodium and produces a large amount of ultra-fine powder, resulting in difficult separation.
Therefore, aiming at the problems of high cost and pollution in the prior art for producing low-sodium high-temperature alumina, a method for preparing low-sodium high-temperature alumina, which is environment-friendly and has cost advantage, is urgently needed to be researched.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for co-producing low-sodium high-temperature alumina by polyaluminium chloride, so as to solve the problems of high cost and serious pollution of the method for preparing the low-sodium alumina in the prior art.
The invention realizes the purpose through the following technical scheme:
the invention provides a method for co-producing low-sodium high-temperature alumina by polyaluminium chloride, which comprises the following steps,
mixing an aluminum hydroxide solution and a hydrochloric acid solution, and then carrying out a dissolution reaction to obtain a polyaluminum chloride solution;
mixing aluminum oxide with the polyaluminium chloride solution, and then carrying out dealkalization-polymerization reaction to obtain a mixed solution;
filtering the mixed solution to obtain a filter cake and a filtrate;
and roasting the filter cake to obtain low-sodium high-temperature alumina, and concentrating the filtrate to obtain the polyaluminium chloride.
Further, the mass ratio of the hydrochloric acid to the aluminum hydroxide is 0.5-3.
Further, the dissolution temperature is 80-160 ℃.
Furthermore, the granularity of the alumina is 10-110 μm.
Further, the specific gravity of the polyaluminium chloride solution is 1.1-1.38 g/ml.
Further, the weight ratio of the polyaluminium chloride solution to the alumina is 2-14.
Further, the dealkalization-polymerization reaction time is 0.5-3.5 h.
Further, the dealkalization-polymerization reaction temperature is 30-110 ℃.
Further, the roasting temperature is 1250-1350 ℃.
The beneficial effects of the invention at least comprise:
the invention provides a method for coproducing low-sodium high-temperature alumina by using polyaluminium chloride, which comprises the steps of mixing an aluminum hydroxide solution and a hydrochloric acid solution, and then carrying out a dissolution reaction to obtain a polyaluminium chloride solution; mixing aluminum oxide with the polyaluminium chloride solution, and then carrying out dealkalization-polymerization reaction to obtain a mixed solution; filtering the mixed solution to obtain a filter cake and a filtrate; and roasting the filter cake to obtain low-sodium high-temperature alumina, and concentrating the filtrate to obtain the polyaluminium chloride. According to the method, a hydrochloric acid solution and aluminum hydroxide are used as raw materials to react to obtain a polyaluminum chloride solution, the polyaluminum chloride solution is an inorganic high polymer material which is generated by the bridging action of hydroxide ions and the polymerization action of polyvalent anions and has a large molecular weight and a high charge, after the aluminum oxide and the polyaluminum chloride solution are mixed, high-charge ions in the polyaluminum chloride replace sodium impurities of the aluminum oxide to enter the solution to form low-charge sodium ions, so that the sodium ions enter a polyaluminum chloride system, the low-sodium aluminum oxide is obtained, and meanwhile, the high-purity polyaluminum chloride is obtained. The method takes industrial alumina as a raw material, has the advantage of cost, is environment-friendly in preparation process, and the prepared alumina has extremely low sodium content.
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In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a process diagram of a method for co-producing low-sodium high-temperature alumina from polyaluminum chloride according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the technical scheme in the embodiment of the invention has the following general idea:
the embodiment of the invention provides a method for coproducing low-sodium high-temperature alumina from polyaluminium chloride, and fig. 1 is a process step diagram of the method for coproducing low-sodium high-temperature alumina from polyaluminium chloride, and with reference to fig. 1, the method comprises the following steps,
and S1, mixing the aluminum hydroxide solution and the hydrochloric acid solution, and then carrying out dissolution reaction to obtain the polyaluminum chloride solution.
Further, the mass ratio of the hydrochloric acid to the aluminum hydroxide is 0.5-3.
The production of the polyaluminium chloride requires strict raw material proportion, and if the quantity ratio of the hydrochloric acid to the aluminum hydroxide exceeds 3, the polyaluminium chloride cannot be produced, but the polyaluminium chloride solution is produced; if the ratio of the amount of hydrochloric acid to aluminum hydroxide is less than 0.5, the viscosity of the resulting polyaluminum chloride slurry is too high to be easily separated.
Further, the dissolution temperature is 80-160 ℃, the dissolution time is 1-3 h, and the dissolution pressure is less than or equal to 0.5 MPa.
The dissolution temperature is high, the polymerization rate is high, and the dissolution rate is high, but the temperature should not be too high in consideration of the cost of heating.
And S2, mixing the aluminum oxide with the polyaluminum chloride solution, and then carrying out dealkalization-polymerization reaction to obtain a mixed solution.
Polyaluminium chloride is an inorganic high molecular material with large molecular weight and high charge generated by the bridging action of hydroxide ions and the polymerization action of polyvalent anions. Sodium impurities in the alumina exist in the form of sodium oxide, after the alumina is mixed with a polyaluminium chloride solution, the sodium oxide impurities can be dissolved in water and react with the water to generate NaOH, and the polyaluminium chloride and the sodium hydroxide undergo dealkalization-polymerization reaction, which specifically comprises the following steps:
m{[Al2(OH)nCl(6-n))]+NaOH}＝m{[Al2(OH)n+1Cl(6-n-1)]+NaCl}
after the alumina is mixed with the polyaluminium chloride solution, the polyaluminium chloride solution reacts with hydroxide in sodium hydroxide to obtain polyaluminium chloride with higher basicity, and sodium ions enter the mixed solution.
Furthermore, the granularity of the alumina is 10-110 μm.
The granularity of the alumina can not be too small, otherwise, the solid-liquid separation after the dealkalization-polymerization reaction is difficult, and if the granularity is too large, the specific area is large, the dealkalization-polymerization reaction speed is slow, the reaction efficiency is low, and the sodium removal effect is influenced.
Further, the specific gravity of the polyaluminium chloride solution is 1.1-1.38 g/ml.
Further, the weight ratio of the polyaluminium chloride solution to the alumina is 2-14.
The weight ratio is more than 14, which causes waste of the polyaluminium chloride solution, and the weight ratio is less than 2, which has poor sodium removal effect.
Further, the dealkalization-polymerization reaction time is 0.5-3.5 h, and the dealkalization-polymerization reaction temperature is 30-110 ℃. The longer the reaction time, the more complete the dealkalization-polymerization reaction proceeds, the better the sodium removal effect, and the lower the sodium content in the alumina, but the dealkalization-polymerization reaction must not be too long in view of the production efficiency. The reaction temperature can influence the speed of dealkalization-polymerization reaction, and the high temperature needs heating and increases the cost, so the reaction temperature is controlled to be 30-110 ℃ measured from the aspects of reaction speed and cost. In the reaction temperature and the reaction time, the sodium removing effect is good, and the economy is achieved.
S3, filtering the mixed solution to obtain a filter cake and a filtrate.
The mixed solution contains high-basicity polyaluminium chloride and alumina, the alumina is insoluble in water, the alumina is filtered to obtain an alumina filter cake and high-basicity polyaluminium chloride filtrate, the filtrate is concentrated to obtain the polyaluminium chloride, the purity of the polyaluminium chloride is high, the total iron content is not more than 0.003%, the basicity is 58-68%, and the density is not less than 1.20g/cm3Can be used as water purifying agent.
S4, roasting the filter cake to obtain low-sodium high-temperature alumina, and concentrating the filtrate to obtain polyaluminium chloride.
Further, the roasting temperature is 1250-1350 ℃.
Through roasting, firstly, water in a filter cake can be removed, and secondly, phase transformation of alumina can be realized to form microcrystalline low-sodium high-temperature alumina. The original plate prepared from the microcrystalline low-sodium high-temperature alumina has the advantages of smoothness, high hardness, uniformity, compactness and high economic benefit. The filtrate may be concentrated by spray drying, or may be concentrated by other methods known in the art. The polyaluminum chloride obtained by concentration has high purity, the indexes of the polyaluminum chloride meet the regulations in GB15892-2009, the regulations of the standards are shown in Table 1, and the polyaluminum chloride can be used as a drinking water purifying agent.
TABLE 1
| Name (R) | Require that |
| Alumina (Al)2O3) Mass fraction/% > or more | 29.0 |
| Degree of basicity/%) | 40.0～90.0 |
| The mass fraction of insoluble substances is less than or equal to | 0.6 |
| pH (10 g/L aqueous solution) | 3.5～5.0 |
| Arsenic (AS) mass fraction/% < or less | 0.0002 |
| Lead (Pb) mass fraction/% < less than or equal to | 0.001 |
| The mass fraction/% of cadmium (Cd) is less than or equal to | 0.0002 |
| The mass fraction of mercury (Hg) is less than or equal to | 0.00001 |
| The mass fraction/%) of hexavalent chromium (Cr +6) is less than or equal to | 0.0005 |
The invention provides a method for coproducing low-sodium high-temperature alumina by polyaluminium chloride, which adopts aluminium hydroxide, a small amount of hydrochloric acid and cheap industrial alumina as raw materials, and has the advantages of exhausted hydrochloric acid after the reaction of the aluminium hydroxide and the hydrochloric acid, and no problem of environmental pollution caused by acid water discharge. The polyaluminium chloride solution and alumina are mixed and then subjected to dealkalization-polymerization treatment, so that the polyaluminium chloride which has high purity and can be used as a water purifying agent and the alumina with low sodium content are obtained. The obtained low-sodium alumina has high purity and uniform primary grain size, and the primary plate prepared from the low-sodium alumina is smooth, high in hardness, uniform and compact, and high in economic benefit.
The technical solution of the present invention will be further described with reference to specific examples.
Example 1
Example 1 provides a method for the co-production of low-sodium high-temperature alumina from polyaluminium chloride, comprising,
and S1, mixing the aluminum hydroxide solution with a hydrochloric acid solution, wherein the mass ratio of hydrochloric acid to aluminum hydroxide is 2, and carrying out dissolution reaction at the temperature of 85 ℃ and the pressure of 0.25MPa for 2.3h to obtain the polyaluminum chloride solution.
And S2, mixing the alumina with the granularity of 20-80 mu m with the polyaluminum chloride solution with the specific gravity of 1.26g/ml obtained in the step S1, wherein the weight ratio of the polyaluminum chloride solution to the alumina is 3, and performing dealkalization-polymerization reaction at 90 ℃ for 2 hours to obtain a mixed solution.
S3, filtering the mixed solution to obtain a filter cake and a filtrate.
S4, roasting the filter cake obtained in the S3 step at 1280 ℃ to obtain low-sodium high-temperature alumina, and spray drying and concentrating the filtrate obtained in the S3 step to obtain polyaluminium chloride.
The indexes of the prepared low-sodium high-temperature alumina are shown in table 2, and the detection indexes of the obtained polyaluminium chloride are shown in table 3.
Example 2
Example 2 provides a method for the co-production of low-sodium high-temperature alumina from polyaluminium chloride, comprising,
and S1, mixing the aluminum hydroxide solution with hydrochloric acid solution, wherein the mass ratio of hydrochloric acid to aluminum hydroxide is 3, and carrying out dissolution reaction at the temperature of 130 ℃ and the pressure of 0.15MPa for 1h to obtain the polyaluminum chloride solution.
And S2, mixing alumina with the particle size of 60-100 mu m with the polyaluminum chloride solution with the specific gravity of 1.18g/ml obtained in the step S1, wherein the weight ratio of the polyaluminum chloride solution to the alumina is 12, and performing dealkalization-polymerization reaction at the temperature of 103 ℃ for 3 hours to obtain a mixed solution.
S3, filtering the mixed solution to obtain a filter cake and a filtrate.
S4, roasting the filter cake at 1340 ℃ to obtain low-sodium high-temperature alumina, and spray-drying and concentrating the filtrate to obtain the polyaluminium chloride.
The indexes of the prepared low-sodium high-temperature alumina are shown in table 2, and the detection indexes of the obtained polyaluminium chloride are shown in table 3.
Example 3
Example 3 provides a method for the co-production of low-sodium high-temperature alumina from polyaluminum chloride, which comprises,
s1, mixing the aluminum hydroxide solution and the hydrochloric acid solution, wherein the mass ratio of hydrochloric acid to aluminum hydroxide is 0.8, and carrying out dissolution reaction at the temperature of 155 ℃ and the pressure of 0.45MPa to obtain the polyaluminum chloride solution.
S2, mixing alumina with the particle size of 60-90 mu m with a polyaluminium chloride solution with the specific gravity of 1.25g/ml, wherein the weight ratio of the polyaluminium chloride solution to the alumina is 8, and carrying out dealkalization-polymerization reaction at the temperature of 40 ℃ for 1h to obtain a mixed solution.
S3, filtering the mixed solution to obtain a filter cake and a filtrate.
S4, roasting the filter cake at the temperature of 1305 ℃ to obtain low-sodium high-temperature alumina, and spray-drying and concentrating the filtrate to obtain the polyaluminum chloride.
The indexes of the prepared low-sodium high-temperature alumina are shown in table 2, and the detection indexes of the obtained polyaluminium chloride are shown in table 3.
Example 4
Example 4 provides a method for the co-production of low-sodium high-temperature alumina from polyaluminum chloride, comprising,
and S1, mixing the aluminum hydroxide solution and the hydrochloric acid solution, wherein the mass ratio of hydrochloric acid to aluminum hydroxide is 1.8, and carrying out dissolution reaction at 105 ℃ and 0.45MPa for 3h to obtain the polyaluminum chloride solution.
S2, mixing alumina with the particle size of 60-100 mu m and a polyaluminium chloride solution with the specific gravity of 1.2g/ml, wherein the weight ratio of the polyaluminium chloride solution to the alumina is 8, and performing dealkalization-polymerization reaction at the temperature of 60 ℃ for 2.8 hours to obtain a mixed solution.
S3, filtering the mixed solution to obtain a filter cake and a filtrate.
S4, roasting the filter cake at the temperature of 1325 ℃ to obtain low-sodium high-temperature alumina, and spray-drying and concentrating the filtrate to obtain the polyaluminum chloride.
The indexes of the prepared low-sodium high-temperature alumina are shown in table 2, and the detection indexes of the obtained polyaluminium chloride are shown in table 3.
Example 5
Example 5 provides a method for the co-production of low-sodium high-temperature alumina from polyaluminum chloride, comprising,
s1, mixing an aluminum hydroxide solution and a hydrochloric acid solution, wherein the mass ratio of hydrochloric acid to aluminum hydroxide is 2.5, and carrying out a dissolution reaction at a temperature of 98 ℃ and a pressure of 0.45MPa for 2.3h to obtain a polyaluminum chloride solution;
s2, mixing alumina with the particle size of 30-80 mu m with a polyaluminium chloride solution with the specific gravity of 1.3g/ml, wherein the weight ratio of the polyaluminium chloride solution to the alumina is 8, and carrying out dealkalization-polymerization reaction at the temperature of 60 ℃ for 2.8h to obtain a mixed solution;
s3, filtering the mixed solution to obtain a filter cake and a filtrate;
s4, roasting the filter cake at 1312 ℃ to obtain low-sodium high-temperature alumina, and spray-drying and concentrating the filtrate to obtain the polyaluminum chloride.
The indexes of the prepared low-sodium high-temperature alumina are shown in table 2, and the detection indexes of the obtained polyaluminium chloride are shown in table 3.
Comparative example 1
Comparative example 1 provides a method for preparing low-sodium alumina, which uses high-purity aluminum hydroxide as a raw material and directly calcines the high-purity aluminum hydroxide at 1220 ℃ to obtain the low-sodium alumina.
The indexes of the low-sodium high-temperature alumina prepared are shown in table 2.
Comparative example 2
Comparative example 2 provides a process for the preparation of low sodium alumina by mixing technical grade alumina as raw material with hydrochloric acid, filtering and calcining at 1280 ℃. The indexes of the low-sodium high-temperature alumina prepared are shown in table 2.
TABLE 2
| Item | Na2Content of O% | Primary grain size, μm |
| Example 1 | 0.07 | 0.5 |
| Example 2 | 0.058 | 0.7 |
| Example 3 | 0.046 | 1.0 |
| Example 4 | 0.049 | 0.8 |
| Example 5 | 0.050 | 0.6 |
| Comparative example 1 | 0.1 | 1.0 |
| Comparative example 2 | 0.3 | 1.2 |
TABLE 3
TABLE 4
Examples 1 to 3 the low sodium high temperature alumina Na prepared2The content of O is 0.046-0.07%, and the primary grain size is 0.5-1.0 μm. Low-sodium high-temperature alumina Na prepared in comparative example 1 and comparative example 22The content of O is 0.1-0.3%, and the primary grain size is 1.0-1.2 μm. Examples 1 to 3 the low-sodium high-temperature alumina Na prepared in examples 1 to 3 was compared with comparative examples 1 and 22The content of O is greatly reduced, and the original grain size is also reduced to a certain degree. The application provides a method for coproducing low-sodium high-temperature alumina from polyaluminium chloride, each index of the polyaluminium chloride prepared by the method meets the requirement of table 1, and the contents of arsenic, lead, cadmium, mercury and hexavalent chromium can only be detected to be qualified due to the limitation of a detection instrument.
By adopting the method provided by the invention, the low-sodium high-temperature alumina can be prepared, the problem of high cost of raw materials for producing the low-sodium high-temperature alumina in the prior art is solved, and the obtained alumina has low impurity sodium content; meanwhile, a high-purity polyaluminium chloride product is obtained, and the product has excellent indexes, meets the requirements of drinking water purifying agents provided by standards, and can be used as a drinking water purifying agent.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for co-producing low-sodium high-temperature alumina by polyaluminium chloride is characterized by comprising the following steps,
mixing an aluminum hydroxide solution and a hydrochloric acid solution, and then carrying out a dissolution reaction to obtain a polyaluminum chloride solution;
mixing aluminum oxide with the polyaluminium chloride solution, and then carrying out dealkalization-polymerization reaction to obtain a mixed solution;
filtering the mixed solution to obtain a filter cake and a filtrate;
and roasting the filter cake to obtain low-sodium high-temperature alumina, and concentrating the filtrate to obtain the polyaluminium chloride.
2. The method for co-producing low-sodium high-temperature alumina by polyaluminum chloride according to claim 1, wherein the mass ratio of the hydrochloric acid to the aluminum hydroxide is 0.5-3.
3. The method for co-producing low-sodium high-temperature alumina by polyaluminium chloride as claimed in claim 1, wherein the dissolution temperature is 80-160 ℃.
4. The method for co-producing low-sodium high-temperature alumina by polyaluminium chloride as claimed in claim 1, wherein the dissolution temperature is 80-160 ℃, the dissolution time is 1-3 h, and the dissolution pressure is less than or equal to 0.5 MPa.
5. The method for co-producing low-sodium high-temperature alumina by polyaluminium chloride as claimed in claim 1, wherein the particle size of the alumina is 10-110 μm.
6. The method for co-producing low-sodium high-temperature alumina by using polyaluminum chloride as claimed in claim 1, wherein the specific gravity of the polyaluminum chloride solution is 1.1-1.38 g/ml.
7. The method for co-producing low-sodium high-temperature alumina from polyaluminum chloride according to claim 1, wherein the weight ratio of the polyaluminum chloride solution to the alumina is 2-14.
8. The method for co-producing low-sodium high-temperature alumina by polyaluminium chloride as claimed in claim 1, wherein the dealkalization-polymerization reaction time is 0.5-3.5 h.
9. The method for co-producing low-sodium high-temperature alumina by polyaluminium chloride as claimed in claim 1, wherein the dealkalization-polymerization reaction temperature is 30-110 ℃.
10. The method for co-producing low-sodium high-temperature alumina by polyaluminium chloride as claimed in claim 1, wherein the roasting temperature is 1250-1350 ℃.
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| CN113493218A (en) * | 2021-08-03 | 2021-10-12 | 重庆工商大学 | High-purity and high-AlbPreparation method of polyaluminium chloride |
| CN113562753A (en) * | 2021-05-12 | 2021-10-29 | 中铝山东新材料有限公司 | Macroporous pseudo-boehmite and preparation method thereof |
| CN114988450A (en) * | 2022-06-17 | 2022-09-02 | 湖北世纪卓霖科技有限公司 | Water treatment centralized station system |
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| CN113493218A (en) * | 2021-08-03 | 2021-10-12 | 重庆工商大学 | High-purity and high-AlbPreparation method of polyaluminium chloride |
| CN114988450A (en) * | 2022-06-17 | 2022-09-02 | 湖北世纪卓霖科技有限公司 | Water treatment centralized station system |
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