CN112591758B

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Info

Publication number: CN112591758B
Application number: CN202110026190.4A
Authority: CN
Inventors: 刘先建; 计文振
Original assignee: Jingdezhen Haoxu Ceramic Material Co ltd
Current assignee: Jingdezhen Haoxu Ceramic Material Co ltd
Priority date: 2021-01-08
Filing date: 2021-01-08
Publication date: 2022-10-28
Anticipated expiration: 2041-01-08
Also published as: CN112591758A

Abstract

The invention relates to a method for efficiently recycling zirconium and silicon in zirconium slag, which comprises the steps of S1, collecting zirconium slag, crushing the zirconium slag into zirconium slag particles, and performing extrusion dehydration on the zirconium slag particles by using rollers to obtain low-chlorine low-water zirconium slag; s2, calcining the low-chlorine low-water zirconium slag at 500-600 ℃ to obtain high-activity zirconium-silicon ash; s3, mixing the high-activity zirconium-silicon ash with liquid caustic soda according to the weight ratio of 1.8-1.2, heating to 55-70 ℃, stirring, and fully reacting to obtain a reaction mixed solution; s4, carrying out cyclone separation on the reaction mixed liquid to obtain a centrifugal liquid and zirconium slurry, and drying and calcining the zirconium slurry to obtain zirconium silicate; s5, mixing and stirring the centrifugal liquid and the micro silicon powder, and adding magnesium oxide to fully obtain a liquid ceramic slurry debonder; according to the method, the zirconium is extracted by using the zirconium slag, and the ceramic slurry liquid dispergator is prepared by using the zirconium extraction tail liquid, so that silicon and water in the zirconium slag are effectively utilized, the zirconium slag is comprehensively and efficiently utilized, and the practical value of the zirconium slag is improved.

Description

Method for efficiently recycling zirconium and silicon in zirconium slag

Technical Field

The invention relates to the technical field of chemical waste recycling, in particular to a method for efficiently recycling zirconium and silicon in zirconium slag.

Background

While the zirconium industry refines various zirconium products, a large amount of zirconium slag is produced. For example, 1.2 tons of zirconium slag are concomitantly produced for every 1 ton of zirconium oxychloride produced. Although some researches and patents on recycling zirconium resources, preparing white carbon black, mesoporous molecular sieve products and the like exist at present, practical application is not available because the content of the effective component zirconium in zirconium slag is too low (the content of zircon sand is lower than 2%, and the content of silicon oxide is lower than 20%), the content of water is too high (more than 65%), and a certain amount of sodium chloride is contained, so that the development and utilization cost is far higher than the benefit. At present, most enterprises still adopt stacking and landfill modes to treat zirconium slag, which not only increases the burden of the enterprises, but also causes serious pollution and damage to the environment. Zirconium slag can not be effectively treated, and becomes a main factor influencing the development of the zirconium industry.

Disclosure of Invention

Aiming at the problem that the development and application value of the zirconium slag is not high at present, the method for preparing the zirconium silicate by using zirconium slag to extract zirconium and preparing the ceramic slurry liquid debonder by using the zirconium slag extraction tail liquid effectively utilizes silicon and water in the zirconium slag, comprehensively and efficiently utilizes the zirconium slag, can extract and recover the zirconium slag to prepare ceramic whitening products, and simultaneously obtains the environment-friendly liquid ceramic slurry debonder by proportioning a proper amount of micro silicon powder to reaction byproducts, thereby greatly improving the practical value of the zirconium slag.

The invention provides a method for efficiently recycling zirconium and silicon in zirconium slag, which comprises the following steps:

s1, collecting zirconium slag, crushing the zirconium slag into zirconium slag particles, and extruding and dehydrating the zirconium slag particles by a pair of rollers to obtain low-chlorine low-water zirconium slag;

s2, calcining the low-chlorine low-water zirconium slag at 500-600 ℃ to obtain high-activity zirconium-silicon ash;

s3, mixing the high-activity zirconium-silicon ash with liquid caustic soda according to the weight ratio of 1.8-1.2, heating to 55-70 ℃, stirring, and fully reacting to obtain a reaction mixed solution;

s4, carrying out cyclone separation on the reaction mixed liquid to obtain a centrifugal liquid and zirconium slurry, and drying the zirconium slurry to obtain zirconium silicate;

and S5, mixing the centrifugal liquid and the micro silicon powder according to the weight ratio of 11.5-9.5, stirring, adding magnesium oxide serving as a catalyst, and fully reacting to obtain the liquid ceramic slurry debonder.

The method comprises the steps of crushing and dehydrating the zirconium slag, particularly the zirconium slag with lower quality (namely the zirconium slag with zircon sand content of less than 2%, silicon oxide content of less than 20% and water content of about 65%), so as to reduce the content of sodium chloride and water in the zirconium slag and improve the composition of the zirconium slag to be beneficial to subsequent reaction; then calcining the low-chlorine low-water zirconium slag into ash, reacting the ash with liquid alkali according to a certain proportion, processing zirconium slurry after reaction liquid separation into zirconium silicate, and reacting the centrifugate with silica fume and magnesium oxide to obtain the dispergator, wherein the magnesium oxide is used as an important catalyst, so that the reaction process can be accelerated, carbon impurities in the dispergator product can be remarkably reduced, and the quality of the dispergator product can be remarkably improved.

Preferably, in the step S1, the zirconium slag particles are 40 mesh or smaller. The reaction speed can be obviously improved, the reaction process is deepened, and the yield is improved.

Preferably, in step S3, the liquid alkali is a 50% sodium hydroxide solution.

Preferably, in the step S3, the weight ratio of the high-activity zirconium silica fume to the liquid caustic soda is 1. The proportion can ensure complete reaction, and simultaneously can save raw materials and reduce cost.

Preferably, in the step S3, the heating is performed to a temperature of 60 ℃.

Preferably, in the step S4, the drying is performed at 100 to 300 ℃.

Preferably, in the step S4, the zirconium silicate may be used for manufacturing whitening products in the ceramic industry.

Preferably, in the step S5, the centrifugate and the silica fume are mixed according to a weight ratio of 10.

Preferably, in the step S5, the magnesium oxide is high-activity magnesium oxide, the particle size of the high-activity magnesium oxide is less than 5um, and the activity marked by citric acid is 10 to 30S. The magnesium oxide as an important catalyst can not only accelerate the reaction process, but also obviously reduce carbon impurities in the dispergator product and obviously improve the quality of the dispergator product. The applicant of the invention finds through research that when the high-activity magnesium oxide is used as a catalyst in the reaction, the reaction time can be shortened by 32.3%, and meanwhile, the high-activity magnesium oxide can also play an adsorption role, so that the content of carbon impurities in a final product is reduced by about 15%, and the product performance is greatly improved.

The invention has the following beneficial effects:

1. the method adopts a more scientific and reasonable method to efficiently recycle the zirconium slag, and the zirconium slag slurry obtained by the reaction of the pretreated high-activity zirconium silicon ash and the liquid alkali is calcined to obtain the zirconium silicate, the whiteness of the zirconium silicate can reach more than 95 ℃, and the zirconium silicate can be used for producing high-end glaze materials, such as ceramic glaze material whitening agents;

2. the invention obtains zirconium silicate, and simultaneously creatively reacts centrifugate obtained by reacting high-activity zirconium silica fume with liquid caustic soda with silica fume and active magnesium oxide to obtain the low-filtrate environment-friendly dispergator, which can be applied to the preparation of slurry in the ceramic industry, such as the preparation of environment-friendly liquid ceramic slurry dispergator.

3. The method effectively utilizes silicon and water in zirconium slag, and obtains a high-quality byproduct ceramic glaze whitening agent and an environment-friendly liquid ceramic slurry debonding agent by a simple process method. Particularly improves the recovery rate of the zirconium slag with lower quality (namely the zirconium slag with zircon sand content lower than 2 percent, silicon oxide content lower than 20 percent and water content of about 65 percent). The method has low investment and convenient operation of production flow, effectively reduces the pollution of zirconium industry to the environment, and effectively realizes the comprehensive efficient utilization of zirconium slag.

Drawings

FIG. 1 is a flow chart of recycling zirconium slag according to the present invention.

Detailed Description

The present invention will be described in further detail with reference to specific examples. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention. The technical means and procedures used in the following examples are conventional means and procedures well known to those skilled in the art, and the raw materials used are commercially available, unless otherwise specified.

Example 1

The zirconium slag was recovered and used as follows.

S1, collecting zirconium slag (the content of zircon sand is 1.8%, the content of silicon oxide is 18.6%), crushing the zirconium slag into 40-mesh zirconium slag particles, and performing extrusion dehydration on the zirconium slag particles by using a pair of rollers to obtain low-chlorine low-water zirconium slag;

s2, calcining the low-chlorine low-water zirconium slag at 550 ℃ to obtain high-activity zirconium-silicon ash;

s3, mixing the high-activity zirconium-silicon ash with 50 liquid caustic soda (namely a sodium hydroxide solution with the mass volume fraction of 50%) according to a weight ratio of 1;

s4, carrying out cyclone separation on the reaction mixed solution to obtain a centrifugal liquid and zirconium slurry, drying the zirconium slurry at 120 ℃, and then calcining at 550 ℃ to obtain zirconium silicate with the whiteness of 96.4;

s5, mixing the centrifugal liquid and the micro silicon powder according to the weight ratio of 10, stirring, adding high-activity magnesium oxide serving as a catalyst, wherein the particle size of the high-activity magnesium oxide is less than 5 microns, the activity marked by citric acid is 15.2S, and fully reacting to obtain the liquid ceramic slurry debonding agent.

Example 2

The zirconium slag is recycled as follows.

S1, collecting zirconium slag (the content of zircon sand is 1.9%, the content of silicon oxide is 19.1%), crushing the zirconium slag into 40-mesh zirconium slag particles, and performing extrusion dehydration on the zirconium slag particles by using a pair of rollers to obtain low-chlorine low-water zirconium slag;

s2, calcining the low-chlorine low-water zirconium slag at 500 ℃ to obtain high-activity zirconium-silicon ash;

s3, mixing the high-activity zirconium silica fume with 50% caustic soda liquid (namely 50% by mass and volume of sodium hydroxide solution) according to a weight ratio of 1;

s4, carrying out cyclone separation on the reaction mixed solution to obtain a centrifugal liquid and zirconium slurry, drying the zirconium slurry at 150 ℃, and then calcining at 500 ℃ to obtain zirconium silicate;

s5, mixing the centrifugate and the silica fume according to a weight ratio of 11.

Example 3

The zirconium slag was recovered and used as follows.

S1, collecting zirconium slag (the content of zircon sand is 1.8%, the content of silicon oxide is 18.2%), crushing the zirconium slag into 40-mesh zirconium slag particles, and performing extrusion dehydration on the zirconium slag particles by using a pair of rollers to obtain low-chlorine low-water zirconium slag;

s2, calcining the low-chlorine low-water zirconium slag at 580 ℃ to obtain high-activity zirconium-silicon ash;

s3, mixing the high-activity zirconium silica fume with 50 parts of liquid caustic soda (namely a sodium hydroxide solution with the mass volume fraction of 50%) according to a weight ratio of 1.2, heating to 70 ℃, stirring, and fully reacting to obtain a reaction mixed solution;

s4, carrying out cyclone separation on the reaction mixed liquid to obtain a centrifugal liquid and zirconium slurry, drying the zirconium slurry at 180 ℃, and then calcining at 500 ℃ to obtain zirconium silicate;

s5, mixing the centrifugal liquid and the micro silicon powder according to a weight ratio of 9.5, stirring, adding high-activity magnesium oxide serving as a catalyst, wherein the particle size of the high-activity magnesium oxide is less than 5um, the activity marked by citric acid is 15.2S, and fully reacting to obtain the liquid ceramic slurry debonding agent.

Example 4

The zirconium slag was recovered and used as follows.

S1, collecting zirconium slag (the content of zircon sand is 2.2%, and the content of silicon oxide is 20.3%), crushing the zirconium slag into 40-mesh zirconium slag particles, and performing extrusion dehydration on the zirconium slag particles by using a pair of rollers to obtain low-chlorine low-water zirconium slag;

s4, carrying out cyclone separation on the reaction mixed solution to obtain a centrifugal liquid and zirconium slurry, drying the zirconium slurry at 200 ℃, and then calcining at 500 ℃ to obtain zirconium silicate;

s5, mixing the centrifugate and the silica fume according to a weight ratio of 10.

The above steps are preferred embodiments of the present patent, but the present patent is not limited to the above embodiments, and those skilled in the art or researchers can make corresponding changes in various knowledge fields without departing from the spirit of the present patent.

Claims

1. A method for efficiently recycling zirconium and silicon in zirconium slag is characterized by comprising the following steps:

s5, mixing the centrifugal liquid and the micro silicon powder according to the weight ratio of 11.5-9.5, stirring, adding magnesium oxide as a catalyst, and fully reacting to obtain the liquid ceramic slurry debonder;

the magnesium oxide is high-activity magnesium oxide, the particle size of the high-activity magnesium oxide is less than 5um, and the activity marked by citric acid is 10-30 s.

2. The method for efficiently recycling zirconium and silicon in zirconium slag according to claim 1, wherein in the step S1, the particles of the zirconium slag are 40 meshes or less.

3. The method for efficiently recycling zirconium and silicon in zirconium slag according to claim 1, wherein in the step S3, the liquid alkali is a sodium hydroxide solution with a concentration of 50%.

4. The method for efficiently recycling zirconium and silicon in zirconium slag according to claim 1, wherein in the step S3, the weight ratio of the high-activity zirconium-silicon ash to the liquid caustic soda is 1.

5. The method for efficiently recycling zirconium and silicon in zirconium slag according to claim 1, wherein in the step S3, the zirconium slag is heated to 60 ℃.

6. The method for efficiently recycling zirconium and silicon in zirconium slag according to claim 1, wherein in the step S4, the drying is performed at 100-300 ℃.

7. The method for efficiently recycling zirconium and silicon in zirconium slag according to claim 1, wherein in the step S4, the zirconium silicate can be used for manufacturing whitening products in the ceramic industry.

8. The method for efficiently recycling zirconium and silicon in zirconium slag according to claim 1, wherein in the step S5, the centrifugate and the micro silicon powder are mixed according to a weight ratio of 10.