CN109721294B - Method for preparing baking-free masonry from newly-generated electrolytic manganese slag - Google Patents
Method for preparing baking-free masonry from newly-generated electrolytic manganese slag Download PDFInfo
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- CN109721294B CN109721294B CN201910100997.0A CN201910100997A CN109721294B CN 109721294 B CN109721294 B CN 109721294B CN 201910100997 A CN201910100997 A CN 201910100997A CN 109721294 B CN109721294 B CN 109721294B
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Abstract
The invention discloses a method for preparing a baking-free masonry from newly-generated electrolytic manganese slag. a. Taking the electrolytic manganese slag, and cleaning the electrolytic manganese slag by adopting clear water to obtain a product A; b. adding the product A into the pretreatment solution, pretreating, and filtering to obtain product B; c. adding cement, a modifier, phosphogypsum, a reinforcing agent and water into the product B, and stirring and mixing to obtain a product C; d. and pressing and forming the product C, and maintaining to obtain a finished product. The invention has the advantages of large mixing amount of electrolytic manganese slag, small negative influence on the prior electrolytic manganese production process, simple process and low cost, and the product can meet the process production requirement, actively promote the benign development of the manganese industry and open up a new way for the comprehensive utilization of the manganese slag.
Description
Technical Field
The invention relates to the fields of metallurgy, chemical industry, building materials, environmental protection and the like, in particular to electrolytic manganese production in the metallurgy field.
Background
At present, the electrolytic manganese production capacity in China is mainly concentrated in places of Ningxia, Guizhou, Hunan, Chongqing, Guangxi, Xinjiang and the like. Except for high-grade Ganna ore used in Ningxia Tianyuan manganese industry, low-grade ore with Mn% of 12-18% is mostly used in the industry, and generally, 7-9 tons of combined slag are generated in each ton of metal manganese. Along with the aggravation of the dilution degree of ores in partial areas in China, the manganese slag quantity per ton is continuously increased, and the manganese slag quantity per ton of a few enterprises exceeds 10 tons. Calculated according to the output of electrolytic manganese metal in 2017, the slag yield in the whole country is about 1200 million tons or more. According to the accumulated calculation of historical yield, the quantity of manganese slag stored in the country exceeds 1 hundred million tons.
Researchers at home and abroad aim at the comprehensive utilization of the electrolytic manganese slag, and develop various researches on the recovery and extraction of valuable metals from the electrolytic manganese slag, the application of the electrolytic manganese slag in the agricultural field, the preparation of cement retarders from the electrolytic manganese slag, the application of the electrolytic manganese slag in paving materials, the application of the electrolytic manganese slag in wall materials, the effect of the electrolytic manganese slag in wastewater treatment, the preparation of baking-free bricks and sintered bricks from the electrolytic manganese slag and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a baking-free masonry body by electrolytic manganese, aiming at the harm caused by the large-scale stockpiling of electrolytic manganese slag. The invention has the characteristics of large mixing amount of electrolytic manganese slag, small negative influence on the existing electrolytic manganese production process, simple process, low cost, capability of meeting the process production requirement of the product, positive promotion of the benign development of the manganese industry and development of a new way for comprehensive utilization of the manganese slag.
The present invention is thus achieved. A method for preparing baking-free masonry from newly-generated electrolytic manganese slag comprises the following steps;
a. taking the electrolytic manganese slag, and cleaning the electrolytic manganese slag by adopting clear water to obtain a product A;
b. adding the product A into the pretreatment solution, pretreating, and filtering to obtain product B;
c. adding cement, a modifier, phosphogypsum, a reinforcing agent and water into the product B, and stirring and mixing to obtain a product C;
d. and pressing and forming the product C, and maintaining to obtain a finished product.
In the method for preparing the baking-free masonry from the newly-generated electrolytic manganese slag, in the step a, the electrolytic manganese slag is cleaned for 3-5 times by adopting clean water.
In the step b, the pretreatment liquid contains one or more of sodium oxide, magnesium oxide and/or calcium oxide, and the pH value of the pretreatment liquid is 8-12.
In the step b, 1 part of the product A is added into 3-6 parts of the pretreatment solution by weight.
In the method for preparing the baking-free masonry from the newly generated electrolytic manganese slag, in the step b, the pretreatment temperature is 20-70 ℃, and the pretreatment time is 3-72 hours.
In the step c, 10-30% of cement, 0.3-10% of hardening and tempering agent, 0-12% of phosphogypsum, 0.05-0.3% of reinforcing agent and 25-30% of water are added into the B product according to mass fraction.
In the method for preparing the baking-free masonry from the newly-generated electrolytic manganese residues, in the step c, the hardening and tempering agent is red mud, and the reinforcing agent is diethylene glycol.
In the method for preparing the baking-free masonry from the newly-generated electrolytic manganese slag, in the step d, the product C is pressed and molded by the pressure of 5-10 Mpa.
In the method for preparing the baking-free masonry from the newly-generated electrolytic manganese slag, in the step d, water is sprayed for maintenance for 25-30 days.
Compared with the prior art, the invention has the following advantages;
1. the invention provides a path for the comprehensive utilization of the electrolytic manganese slag on one hand, expands the sources and the types of the building material raw materials on the other hand, reduces the treatment cost of the electrolytic manganese slag, actively promotes the benign development of the manganese industry, and opens up a new way for the comprehensive utilization of the manganese slag;
2. the method mainly comprises the steps of washing, pretreating, uniformly mixing, stirring, briquetting and maintaining the electrolytic manganese slag, wherein soluble substances in the electrolytic manganese slag are cleaned in the step a; b, exciting the cleaned electrolytic manganese slag to reconstruct an ore phase of the cleaned electrolytic manganese slag, wherein the original electrolytic manganese slag has no volcanic ash activity, and obtaining slag with the volcanic ash activity through the treatment for preparing the baking-free masonry; in the step C, adding cement, a modifier, phosphogypsum, a reinforcing agent and water into the product B, and stirring and mixing by adopting the conventional technology to obtain a product C; in the step d, pressing and forming the product C by adopting the conventional technology, and maintaining to obtain a finished product; in the process, the invention has no high-temperature and high-pressure equipment and has simple process;
3. the technology of the invention has independent treatment, is not connected with the electrolytic manganese system greatly, does not have impact influence on the process, has no influence on materials and process parameters, and has the advantage of small negative influence on the existing electrolytic manganese production process;
4. the existing report reports that the doping amount of the electrolytic manganese slag of the masonry is less than 30 percent, and the doping amount of the invention is about 80 percent, so the cost of the masonry can be greatly reduced, and the electrolytic manganese slag can be utilized as a waste, thereby having the advantage of low cost.
Experiments prove that:
1. the applicant respectively carries out strength detection on the unfired masonry finished product prepared in the embodiment of the invention, and the detection results are shown in the following table:
the above table shows that the strength of the finished product of the baking-free masonry reaches 8-15Mpa, and the strength of the existing sintered clay brick is 10Mpa, so that the strength of the baking-free masonry prepared by the invention is high, the production requirements of the baking-free masonry process can be met, the product application is wide, the market prospect is good, the benign development of the manganese industry is actively promoted, and a new way is opened for the comprehensive utilization of manganese slag.
In conclusion, the invention has the advantages of large mixing amount of electrolytic manganese slag, small negative influence on the existing electrolytic manganese production process, simple process and low cost, and the product can meet the process production requirement, actively promote the benign development of the manganese industry and open up a new way for the comprehensive utilization of the manganese slag.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1. A method for preparing baking-free masonry from newly-generated electrolytic manganese slag comprises the following steps;
a. taking 500kg of electrolytic manganese slag, and cleaning the electrolytic manganese slag for 3 times by adopting clear water to obtain a product A;
b. adding 1 part of the product A into 3 parts of pretreatment liquid according to the weight of the product A in parts by weight, wherein the pretreatment temperature is 20 ℃, and the pretreatment time is 3 hours, and then filtering to obtain a product B; wherein the pretreatment solution contains sodium oxide, and the pH value of the pretreatment solution is 8;
c. according to the weight of the B product, adding 10% of cement, 0.3% of modifying agent, 0.05% of reinforcing agent and 25% of water into the B product by mass fraction, and stirring and mixing to obtain a C product; wherein the modifying agent is red mud, and the reinforcing agent is diethylene glycol;
d. and pressing and molding the product C under the pressure of 5Mpa, and spraying water for maintaining for 25 days to obtain a finished product.
Example 2. A method for preparing baking-free masonry from newly-generated electrolytic manganese slag comprises the following steps;
a. taking 500kg of electrolytic manganese slag, and cleaning the electrolytic manganese slag for 4 times by adopting clear water to obtain a product A;
b. adding 1 part of the product A into 4 parts of pretreatment liquid according to the weight of the product A, wherein the pretreatment temperature is 30 ℃, and the pretreatment time is 15 hours, and then filtering to obtain a product B; wherein the pretreatment liquid contains sodium oxide and magnesium oxide, and the pH value of the pretreatment liquid is 9;
c. according to the weight of the product B, adding 15% of cement, 3% of a modifying agent, 3% of phosphogypsum, 0.1% of a reinforcing agent and 26% of water into the product B by mass fraction, and stirring and mixing to obtain a product C; wherein the modifying agent is red mud, and the reinforcing agent is diethylene glycol;
d. and pressing and molding the product C under 6Mpa, and spraying water for maintaining for 26 days to obtain the final product.
Example 3. A method for preparing baking-free masonry from newly-generated electrolytic manganese slag comprises the following steps;
a. taking 500kg of electrolytic manganese residues, and cleaning the electrolytic manganese residues with clear water for 5 times to obtain a product A;
b. adding 1 part of the product A into 5 parts of pretreatment liquid according to the weight of the product A, wherein the pretreatment temperature is 45 ℃, and the pretreatment time is 30 hours, and then filtering to obtain a product B; wherein the pretreatment liquid contains sodium oxide, magnesium oxide and calcium oxide, and the pH value of the pretreatment liquid is 10;
c. according to the weight of the product B, adding 20% of cement, 6% of modifying agent, 7% of phosphogypsum, 0.2% of reinforcing agent and 27% of water into the product B by mass fraction, and stirring and mixing to obtain a product C; wherein the modifying agent is red mud, and the reinforcing agent is diethylene glycol;
d. and pressing and molding the product C under the pressure of 7Mpa, and spraying water for 27 days to obtain a finished product.
Example 4. A method for preparing baking-free masonry from newly-generated electrolytic manganese slag comprises the following steps;
a. taking 500kg of electrolytic manganese slag, and cleaning the electrolytic manganese slag for 4 times by adopting clear water to obtain a product A;
b. adding 1 part of the product A into 4 parts of pretreatment liquid according to the weight of the product A, wherein the pretreatment temperature is 50 ℃, and the pretreatment time is 50 hours, and then filtering to obtain a product B; wherein the pretreatment liquid contains magnesium oxide and calcium oxide, and the pH value of the pretreatment liquid is 11;
c. according to the weight of the product B, adding 25% of cement, 8% of modifying agent, 9% of phosphogypsum, 0.25% of reinforcing agent and 29% of water into the product B by mass fraction, and stirring and mixing to obtain a product C; wherein the modifying agent is red mud, and the reinforcing agent is diethylene glycol;
d. and pressing and molding the product C under the pressure of 8Mpa, and spraying water for maintenance for 29 days to obtain a finished product.
Example 5. A method for preparing baking-free masonry from newly-generated electrolytic manganese slag comprises the following steps;
a. taking 500kg of electrolytic manganese residues, and cleaning the electrolytic manganese residues with clear water for 5 times to obtain a product A;
b. adding 1 part of the product A into 6 parts of pretreatment liquid according to the weight of the product A, wherein the pretreatment temperature is 70 ℃, and the pretreatment time is 72 hours, and then filtering to obtain a product B; wherein the pretreatment liquid contains sodium oxide, magnesium oxide and calcium oxide, and the pH value of the pretreatment liquid is 12;
c. according to the weight of the product B, adding 30% of cement, 10% of modifying agent, 12% of phosphogypsum, 0.3% of reinforcing agent and 30% of water into the product B by mass fraction, and stirring and mixing to obtain a product C; wherein the modifying agent is red mud, and the reinforcing agent is diethylene glycol;
d. and pressing the product C under 10Mpa, and spraying water for 30 days to obtain the final product.
Claims (3)
1. A method for preparing baking-free masonry from newly-generated electrolytic manganese slag is characterized by comprising the following steps: the preparation method comprises the following steps;
a. taking the electrolytic manganese slag, and cleaning the electrolytic manganese slag by adopting clear water to obtain a product A;
b. adding the product A into the pretreatment solution, pretreating, and filtering to obtain product B;
c. adding cement, a modifier, phosphogypsum, a reinforcing agent and water into the product B, and stirring and mixing to obtain a product C;
d. pressing and forming the product C, and maintaining to obtain a finished product;
in the step a, cleaning the electrolytic manganese slag for 3-5 times by adopting clear water;
in the step b, the pretreatment solution contains one or more of sodium oxide, magnesium oxide and/or calcium oxide, and the pH value of the pretreatment solution is 8-12;
in the step b, 1 part of the product A is added into 3 to 6 parts of the pretreatment solution by weight;
in the step b, the pretreatment temperature is 20-70 ℃, and the pretreatment time is 3 hours;
in the step c, 10-30% of cement, 0.3-10% of modifying agent, 0-12% of phosphogypsum, 0.05-0.3% of reinforcing agent and 25-30% of water are added into the B product according to mass fraction;
in the step c, the hardening and tempering agent is red mud, and the reinforcing agent is diethylene glycol.
2. The method for preparing the baking-free masonry from the newborn electrolytic manganese slag according to claim 1, which is characterized by comprising the following steps: and in the step d, the product C is pressed and molded by the pressure of 5-10 Mpa.
3. The method for preparing the baking-free masonry from the newborn electrolytic manganese slag according to claim 1, which is characterized by comprising the following steps: and d, in the step d, maintaining for 25-30 days by adopting water spraying.
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| CN112624651A (en) * | 2021-01-26 | 2021-04-09 | 中南大学 | Resource utilization method of electrolytic manganese filter-pressing residues |
| CN113248163A (en) * | 2021-05-19 | 2021-08-13 | 贵州大学 | Preparation method of electrolytic manganese slag phosphogypsum composite cementing material |
| CN116082011A (en) * | 2022-12-27 | 2023-05-09 | 贵州大学 | Aerated concrete block produced from electrolytic manganese slag and preparation method thereof |
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| JP2714875B2 (en) * | 1990-06-22 | 1998-02-16 | 宇部興産株式会社 | Blast furnace slag crushing method |
| CN101314530A (en) * | 2008-07-07 | 2008-12-03 | 昆明理工大学 | Method for producing building material with low-temperature ceramic modified industry by-product gypsum |
| CN101570037B (en) * | 2009-06-01 | 2013-06-05 | 中国环境科学研究院 | Method for preparing construction material by utilizing electrolytic manganese slag |
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