CN111302391B - Method for preparing small pellet material for fluidized bed chlorination furnace from full-high titanium slag - Google Patents
Method for preparing small pellet material for fluidized bed chlorination furnace from full-high titanium slag Download PDFInfo
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Abstract
The invention discloses a method for preparing a small pellet material for a fluidized bed chlorination furnace from full-high titanium slag, which comprises the steps of mixing fine-grain high titanium slag, an organic binder I consisting of biomass oil, sodium humate and amino acid and water to obtain a mixture; after the mixture is finely ground, pelletizing, spraying an organic binder II solution consisting of biomass oil, sodium humate, amino acid and metal chloride salt with more than two valences into the mixture in the pelletizing process, and drying and roasting the obtained green pellets to obtain small pellets for the fluidized bed chlorination furnace, wherein the small pellets have high strength and high titanium grade; the method solves the problem of poor green pellet quality when the high titanium slag which is difficult to pelletize is used for preparing the small pellets for the fluidized bed chlorination furnace, has the advantage of low cost, can improve the titanium grade by more than 0.5 percent when the prepared small pellet material is used for the production process of titanium dioxide by the chlorination process, and can meet the production requirements on green pellet strength and roasted pellet strength.
Description
Technical Field
The invention relates to a preparation method of a small pellet for a boiling chlorination furnace, in particular to a method for preparing a small pellet for a boiling chlorination furnace by using refractory full-high titanium slag, belonging to the technical field of preparation of high-quality furnace burden in metallurgical engineering.
Background
At present, the industrial titanium dioxide production Process mainly comprises a sulfuric acid Process (SP-sulfate Process) and a chlorination Process (CP-chlorination Process). The sulfuric acid process production technology is generated in the early 18 th century and is industrialized in the 30 th century. However, as the awareness of environmental protection of human beings increases, the environmental problems are increasingly highlighted. The chlorination process invented in the 70's of the 20 th century gradually replaced the sulfuric acid process, and the chlorination process has dominated industrial production.
The production process of titanium dioxide by chlorination method mainly comprises three procedures: (1) high-grade natural rutile or artificial titanium-rich material is used as a raw material, and a chlorination process is adopted to produce crude titanium tetrachloride; then refined titanium tetrachloride is obtained through purification and refining. (2) The titanium dioxide is prepared by the gas phase oxidation of refined titanium tetrachloride. (3) The titanium dioxide is post-treated to prepare titanium white. Titanium tetrachloride is used as an intermediate product in the titanium dioxide production process, and the main production modes of titanium tetrachloride comprise molten salt chlorination and boiling chlorination, wherein the boiling chlorination has the advantages of high production efficiency, low cost, small environmental pollution, high automation degree and the like, and becomes a mainstream mode of titanium tetrachloride production. Boiling chlorination, also called fluidization chlorination, is to suspend solid particle groups by utilizing the action of flowing fluid, so that the solid particles have the characteristics shown by certain fluids, thereby strengthening the contact process between gas and solid or between liquid and solid.
The high titanium slag is commonly known as titanium ore concentrate formed by a physical production process, and the titanium ore is heated and melted by an electric furnace, so that titanium dioxide and iron in the titanium ore are melted and separated to obtain the concentrate with high titanium dioxide content. The high titanium slag is neither waste slag nor by-product, but is high-quality raw material for producing titanium tetrachloride, titanium white and titanium sponge products. At present, in the process of producing titanium tetrachloride by boiling chlorination, high titanium slag and petroleum coke are mixed according to a certain proportion at a high temperature to prepare a blocky material, and then chlorination is carried out in a boiling chlorination furnace. In a boiling chlorination furnace, the energy consumption, the pollution and the reaction of blocky materials are large in the chlorination process. Pan Steel group Korea koxi et al (CN101649392A) discloses a pelletizing method of titanium concentrate and a pelletizing binder, which can remarkably reduce the influence of lower titanium grade in the smelting process. The patent (CN107954472A) discloses a titanium dioxide production process, which mainly comprises chlorination, oxidation and post-treatment sections, and has the advantages of simple process operation and lower cost.
The method for directly forming the pellets for the fluidized bed chlorination furnace by using the high titanium slag is not mentioned in the methods, because the high titanium slag has coarse granularity and extremely poor hydrophobicity and is difficult to form the pellets; in addition, due to the special gas dynamic requirements of the boiling chlorination furnace, the particle size of the pellets fed into the furnace is strictly limited, and the fed materials need to be controlled to be smaller in size; however, the prior art has difficulty in preparing small-sized pellets using high titanium slag having high hydrophobicity. Therefore, the development of the method for preparing the small pellet material for the boiling chlorination furnace from the full-high titanium slag is of great significance.
Disclosure of Invention
Aiming at the technical problems of high energy consumption, easy pollution, low utilization rate of raw materials, difficulty in preparing small-size pellet materials from high-hydrophobicity high titanium slag and the like in the chlorination process of the existing high titanium slag in a fluidized bed chlorination furnace, the invention aims to provide a method for preparing the high-strength and high-grade small pellet materials for the fluidized bed chlorination furnace from the high-titanium slag which is difficult to pelletize by using a special organic binder and combining a special pelletizing process, when the small pellet materials prepared by the method are used for the production process of titanium dioxide by a chlorination method, the titanium grade can be improved by more than 0.5 percent, and the green pellet strength and the roasted pellet strength can meet the production requirements of the fluidized bed chlorination furnace.
In order to realize the technical purpose, the invention provides a method for preparing a small pellet material for a fluidized bed chlorination furnace from full-high titanium slag, which comprises the steps of mixing fine-grain high titanium slag, an organic binder I and water to obtain a mixture; after the mixture is finely ground, pelletizing, spraying an organic binder II solution into the mixture in the pelletizing process, and drying and roasting the obtained green pellets to obtain small pellet materials for the fluidized bed chlorination furnace;
the organic binder I consists of biomass oil, sodium humate and amino acid;
The organic binder II solution contains organic binder II consisting of biomass oil, sodium humate, amino acid and metal chloride salt with the valence of more than two.
According to the technical scheme, the biomass oil and the humic acid sodium of the organic binder I are macromolecular substances containing a large number of oxygen-containing functional groups, the types and the number of the functional groups are large, the functional groups comprise carboxyl and hydroxyl active functional groups which are favorable for generating strong chemical adsorption with the surface of the high-titanium slag, esters, ethers and the like, and the binding performance between minerals is enhanced; the amino acid simultaneously contains amino and carboxyl micromolecules, the amino generates a slightly alkaline environment on the surface of the high titanium slag particles, a chelate is easily formed with metal ions on the surface of the high titanium slag, the action of the binder on the particle surface and the action between the particles are enhanced, and the amino and the carboxyl can generate ionic bond combination, so that the combination property between the high titanium slag raw material particles can be further improved by utilizing the amino acid; therefore, under the synergistic effect of the three components, the high titanium slag raw materials generate strong chemisorption and chelation, and have good balling property and strength.
In the technical scheme of the invention, the organic binder is prepared by adding a metal chloride salt component with a high boiling point and more than two valences on the basis of the binder I. On one hand, the surface of the high titanium slag particles is smooth, the amount of metal ions is small, and the metal ions of the metal chloride salt with more than two valences in a solution system are hydrolyzed and adsorbed on the surfaces of the high titanium slag particles, so that the surface effects of the biomass oil, the sodium humate, the amino acid and the high titanium slag particles can be enhanced; on the other hand, the addition of the metal chloride with high boiling point and more than divalent does not bring impurities with similar boiling point to the titanium tetrachloride into a boiling chlorination system, thereby simplifying the subsequent rectification process of the titanium tetrachloride.
The technical scheme of the invention is that the binder is added in two steps, the binder I and the high titanium slag in the first step can realize the pre-wetting of the high titanium slag and the enhancement of the acting force of the binder and the surface interface of the particles in the presence of a small amount of water and in the environment of mechanical grinding and strong stirring and mixing; the second step of the adhesive II realizes the rapid balling of the high titanium slag material under the combined action of more water and inorganic chloride ions, and ensures that the balling has higher strength.
As a preferable scheme, the organic binder I consists of biomass oil, sodium humate and amino acid in parts by mass as follows: 5-30 parts of biomass oil; 65-90 parts of humic acid sodium; 1-5 parts of amino acid. The organic binder I provided by the technical scheme of the invention adopts sodium humate and biomass oil high molecules as main components of the organic binder, and utilizes rich oxygen-containing polar groups between the two components to synergistically improve the binding performance of the high-titanium raw material particles, on the basis, a small amount of alkaline amino acid is added, so that a good bridging effect and a good chelating effect can be achieved, the binding performance of the high-titanium raw material particles is enhanced, and the chemical effect of the biomass oil and the sodium humate on the surfaces of the high-titanium raw material particles is better exerted. In the formula of the organic binder, the proportion of the biomass oil and the sodium humate needs to be proper, the biomass oil is a high polymer with strong acidity, the proportion cannot be too high and is mainly controlled to be 5-30 parts, so that the proportion of the sodium humate with weak acidity as a main component is as high as 65-90 parts, the synergistic effect of the biomass oil and the sodium humate can be well exerted, and the amino acid mainly plays a role in strengthening the bonding effect of the biomass oil and the sodium humate amino acid, so that the addition amount of the amino acid is controlled to be within 1-5 parts, the bonding performance is further improved, but the biomass oil and the sodium humate polymer which are rich in oxygen-containing groups still play a main bonding effect, and therefore, the proportion of the amino acid of small molecules is too high, the proportion of the biomass oil and the sodium humate can be reduced, and the bonding performance can be reduced.
As a preferred embodiment, the ash content of sodium picrorhizae in the organic binder I is not higher than 20%. The humic acid sodium is mainly derived from lignite, is cheap coal-based humic acid, is used as a main raw material of an organic binder, and accords with the concept of green development.
In a preferred embodiment, the biomass oil in the organic binder I is a pyrolysis oil of at least one biomass selected from corn, cotton, rape, wheat, rice plant stalks, corn cobs, peanut shells and coconut shells. The biomass oil is a mixture consisting of various degradation products of cellulose, hemicellulose and lignin, the prior art mainly uses the biomass oil as liquid fuel, and the biomass oil is used as a binder component for preparing high-titanium slag pellets.
As a preferred embodiment, the amino acid in the organic binder I is glycine and/or glutamic acid. The glycine and the glutamic acid can generate a slightly alkaline environment to form a very strong chelate with metal ions on the surface of the high titanium slag, so that the pelletizing rate and the pelletizing strength of the high titanium slag raw material can be obviously improved.
As a preferable scheme, the addition amount of the organic binder I is 0.5-1.8% of the mass of the fine-grained high-titanium slag.
Preferably, the addition amount of the water accounts for 1-3% of the mass of the mixture.
As a preferable scheme, the fine-grained high-titanium slag meets the condition that the mass percentage of-200-mesh fraction is not less than 80 percent, and the specific surface area is not less than 1650cm 2 (ii) in terms of/g. The fine-grain high-titanium slag is prepared by ball-milling the high-titanium slag to a proper granularity in advance so as to improve the specific surface area and facilitate full contact with an organic binder.
As a preferable scheme, the organic binder II comprises biomass oil, sodium humate, amino acid and metal chloride salt with more than two valences according to the following components in parts by mass: 5-30 parts of biomass oil, 65-85 parts of humic acid sodium, 1-5 parts of amino acid and 1-5 parts of divalent or higher metal chloride.
The organic binder II provided by the technical scheme of the invention is introduced with metal chloride with more than two valences on the basis of the binder I, and is mainly used for modifying the surface of high-titanium slag particles and strengthening the surface effects of biomass oil, sodium humate, amino acid and the high-titanium slag particles.
As a preferred scheme, the ash content of the sodium picrorhizae in the organic binder II is not higher than 20%;
as a preferred scheme, the biomass oil in the organic binder II is pyrolysis oil of at least one biomass selected from corn, cotton, rape, wheat, rice plant straw, corn cob, peanut shell and coconut shell;
As a preferred embodiment, the amino acid in the organic binder II is glycine and/or glutamic acid;
in a preferred embodiment, the divalent or higher metal chloride salt of the organic binder II includes at least one of ferric chloride, calcium chloride, magnesium chloride, and manganese chloride.
Preferably, the organic binder II is sprayed in the form of organic binder II solution with the concentration of 1 g/L-20 g/L, and the addition amount of the organic binder II is 6% -9% of the green pellet water content.
As a preferable scheme, the granularity of the fine grinding control mixture is 100 percent of-200 meshes, and the mass percent of-325 meshes is not less than 75 percent.
As a preferred scheme, the system of drying and roasting the green pellets is as follows: the drying temperature is 100-200 ℃, and the drying time is 30-60 min; the roasting temperature is 800-1000 ℃, and the roasting time is 10-30 min.
As a preferable scheme, the particle size of the green pellets is controlled to be 0.05 mm-2.0 mm. The method can realize the controllable grain diameter of the green pellets so as to obtain the green pellets with small grain diameter according to the requirement.
As a preferable scheme, the fine grinding process adopts a planetary ball mill, and the fine grinding mixture is obtained by a positive and negative alternative ball milling mode, wherein the rotating speed of the planetary ball mill is 300-700 r/min, and the ball milling time is 5-30 min. The function between the binder and the fine-grained high-titanium slag can be strengthened by ball milling.
As a preferable scheme, the green pellets are prepared by a disc type pelletizer, and the aqueous solution of the binder II is uniformly sprayed on the raw materials in a spraying mode in the pelletizing process, wherein the rotating speed of the disc type pelletizer is 20 r/min-35 r/min. The particle size of the green pellets is 0.05 mm-2.0 mm.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the technical scheme of the invention solves the technical problem that high titanium slag is difficult to form pellets due to strong hydrophobicity in the prior art, and the special binder is combined with the special pelletizing process, so that the high-strength pellet material for the fluidized bed chlorination furnace can be obtained, the size of green pellets can be controlled, the pollution and energy consumption of a chlorination working section in titanium dioxide production are reduced, the utilization rate of raw materials is improved, and the safety coefficient of the fluidized bed chlorination furnace is improved.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be noted that these examples are only for better understanding of the present invention, and do not limit the scope of the present invention.
Comparative example 1
The binder in this comparative example was a conventional single sodium carboxymethylcellulose.
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content was 87%. Firstly, high titanium slag (the specific surface area is 1760 cm) with the grain size of less than-0.074 mm accounting for 85 percent 2 The mixture is mixed by the following raw materials of the raw materials. And performing positive and negative alternate ball milling on the primary mixture by using a planetary ball mill, wherein the rotating speed of the planetary ball mill is 400r/min, and the ball milling time is 30min, so as to obtain a secondary mixture. And spraying a sodium carboxymethylcellulose solution with the concentration of 5g/L into the mixture. Pelletizing by a disc pelletizer, wherein the rotating speed of the disc pelletizer is 30r/min, and pelletizingThe water content of the green ball is 8.5% by adding water in the process. The ball forming rate of the obtained green ball is only 50%. After the product balls are dried for 60min at 120 ℃, the obtained dried pellets are vibrated for 300 times by a vibrating screen machine, and the particle size is up to 75% below 0.05mm after vibration. Roasting at 900 deg.c for 30min to obtain roasted pellet with strength of 800N. But green balls have poor strength.
Comparative example 2
In this comparative example, no binder I was added to the mix.
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content was 88.2%. High titanium slag (specific surface area 1760 cm) with the grain size less than-0.074 mm (85wt percent) 2 Adding 1.5% of water, and performing positive and negative alternate ball milling by using a planetary ball mill, wherein the rotating speed of the planetary ball mill is 400r/min, the ball milling time is 30min, so as to obtain a mixture with the mass percentage of-200 meshes being 100% and the mass percentage of-325 meshes being 75%. Pelletizing the mixture by a disc pelletizer, and spraying 5g/L organic binder II (5% of biomass oil, 85% of sodium humate, 5% of glycine and FeCl) into the mixture in the pelletizing process 3 5%) water solution, so that the water content of the green ball is 9%, wherein the rotating speed of the disc type granulator is 30 r/min. The ball forming rate of the obtained green ball is only 60%. After the product balls are dried for 60min at 120 ℃, the obtained dried pellets are vibrated for 300 times by a vibrating screen machine, and the particle size is up to 50% below 0.05mm after vibration. After being roasted for 30min at 900 ℃, the strength of the roasted ball is only 500N. The use requirement of the boiling chlorination furnace is difficult to achieve.
Comparative example 3
No biomass oil was added to the mix in this comparative example.
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content was 86.8%. To high titanium slag (specific surface area 1650 cm) with the grain size less than-0.074 mm (80wt percent) 2 Adding 0.7 percent of organic binder I (the content of sodium humate is 95 percent, the content of glutamic acid is 5 percent) and 2 percent of water into the mixture, uniformly mixing the mixture, and performing positive and negative alternate ball milling by using a planetary ball mill, wherein the rotating speed of the planetary ball mill is 400r/min, the ball milling time is 30min, and the mass of the obtained product in the mass percentage of-200 meshes is obtained The secondary mixture accounts for 76 percent of the-325-mesh fraction when the ratio is 100 percent. Pelletizing the mixture by a disc pelletizer, wherein the rotating speed of the disc pelletizer is 30r/min, and organic binder II (95% of sodium humate, 2% of glycine and FeCl) with the concentration of 5g/L is sprayed into the mixture in the pelletizing process 3 1％，MnCl 2 1％，MgCl 2 1%) aqueous solution, so that the green pellet contains 7.5% water. The ball forming rate of the obtained green ball is only 50%. Drying the green pellets in an oven at 120 ℃ for 60min, and vibrating the obtained dried pellets by a vibrating screen for 300 times, wherein the particle size of the dried pellets is up to 20% below 0.05mm after vibration. Roasting at 950 deg.c for 30min to obtain roasted pellet with average strength of 800N. The green pellet has poor quality and cannot meet the requirements of a boiling chlorination furnace.
Comparative example 4
No chloride salt was added to binder II in this comparative example.
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content is 85.0%. To high titanium slag (specific surface area 1790 cm) with the grain size less than-0.074 mm (88wt percent) 2 Adding 1.5 percent of organic binder I (5 percent of biomass oil, 90 percent of sodium humate and 5 percent of glutamic acid) and 3 percent of water into the mixture, uniformly mixing the mixture, and performing forward and backward alternate ball milling by using a planetary ball mill, wherein the rotating speed of the planetary ball mill is 400r/min, and the ball milling time is 30min, so as to obtain a secondary mixture, wherein the mass percentage of-200-mesh fraction is 100 percent, and the mass percentage of-325-mesh fraction is 75 percent. Pelletizing the mixture by a disc pelletizer, wherein the rotating speed of the disc pelletizer is 30r/min, and spraying organic binder II (15% of biomass oil, 81% of sodium humate and 4% of glutamic acid) with the concentration of 10g/L into the mixture in the pelletizing process to ensure that the water content of the green pellets is 8.2%. The ball forming rate of the obtained green ball is only 70%. Drying the green pellets in an oven at 120 ℃ for 60min, and vibrating the obtained dried pellets by a vibrating screen for 300 times, wherein the particle size of the dried pellets is up to 25% below 0.05mm after vibration. The green pellet has poor quality and does not meet the chlorination requirement of a boiling chlorination furnace.
Comparative example 5
The binder in this comparative example did not add amino acids.
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content is 85.0%. To high titanium slag (specific surface area 1790 cm) with the grain size less than-0.074 mm (88wt percent) 2 Adding 1.8% of organic binder I (15% of biomass oil and 85% of sodium humate) and 3% of water into the mixture per gram, uniformly mixing, and performing forward and reverse alternate ball milling by using a planetary ball mill, wherein the rotating speed of the planetary ball mill is 400r/min, and the ball milling time is 30min, so as to obtain a secondary mixture, wherein the mass percentage of-200-mesh fraction is 100%, and the mass percentage of-325-mesh fraction is 80%. Pelletizing the mixture by a disc pelletizer, wherein the rotating speed of the disc pelletizer is 30r/min, and organic binder II (10% of biomass oil, 86% of sodium humate and FeCl) with the concentration of 12g/L is sprayed into the mixture in the pelletizing process 3 2％，MnCl 2 2%) so that the green pellets had a water content of 8.5%. The green pellet obtained had a pellet forming rate of only 74%. Drying the green pellets in an oven at 120 ℃ for 60min, and vibrating the obtained dried pellets by a vibrating screen for 300 times, wherein the particle size of the dried pellets is up to 21% below 0.05mm after vibration. The green pellet has poor quality and does not meet the chlorination requirement of a boiling chlorination furnace.
Example 1
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content was 86.8%. To high titanium slag (specific surface area 1650 cm) with the grain size less than-0.074 mm (80wt percent) 2 Adding 0.7 percent of organic binder I (20 percent of biomass oil, 75 percent of sodium humate, 2 percent of glutamic acid and 3 percent of glycine) and 2 percent of water into the mixture, uniformly mixing the mixture, and performing forward and backward alternate ball milling by using a planetary ball mill, wherein the rotating speed of the planetary ball mill is 400r/min, the ball milling time is 30min, so as to obtain a secondary mixture, wherein the mass percent of-200-mesh fraction is 100 percent, and the mass percent of-325-mesh fraction is 76 percent. Pelletizing the mixture by a disc pelletizer, wherein the rotating speed of the disc pelletizer is 30r/min, and organic binder II (20% of biomass oil, 70% of sodium humate, 5% of glutamic acid and 5% of FeCl) with the concentration of 5g/L is sprayed into the mixture in the pelletizing process 3 2％，MnCl 2 2％，MgCl 2 1%) aqueous solution, so that the green ball has a water content of7.5 percent. The yield of the green pellets was 80%. The green pellets are dried in an oven at 120 ℃ for 60min, the obtained dried pellets are vibrated for 300 times by a vibrating screen machine, and the size fraction below 0.05mm is only 5 percent after vibration. Roasting at 900 deg.c for 30min to obtain roasted balls with average strength of 900N. The pellet meets the chlorination requirement of a boiling chlorination furnace.
Example 2
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content is 85.0%. To high titanium slag (specific surface area 1760 cm) with the grain size less than-0.074 mm (85wt percent) 2 Adding 1.0% of organic binder I (5% of biomass oil, 90% of sodium humate and 5% of glutamic acid) and 2% of water into the mixture, uniformly mixing the mixture, and performing forward and reverse alternate ball milling by using a planetary ball mill, wherein the rotating speed of the planetary ball mill is 400r/min, and the ball milling time is 30min, so as to obtain a secondary mixture, wherein the mass percentage of-200-mesh fraction is 100%, and the mass percentage of-325-mesh fraction is 85%. Pelletizing the mixture by a disc pelletizer, wherein the rotating speed of the disc pelletizer is 30r/min, and organic binder II (15% of biomass oil, 80% of sodium humate, 4% of glutamic acid and FeCl) with the concentration of 10g/L is sprayed into the mixture in the pelletizing process 3 1%) so that the green pellets contained 6% of water. The yield of the green pellets was 85%. The green pellets are dried in an oven at 120 ℃ for 60min, the obtained dried pellets are vibrated for 300 times by a vibrating screen machine, and the size fraction below 0.05mm is only 3 percent after vibration. Roasting at 980 deg.c for 25min to obtain roasted pellet with average strength of 1050N. The pellet meets the chlorination requirement of a boiling chlorination furnace.
Example 3
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content was 88.4%. To high titanium slag (specific surface area 1820 cm) with the grain size less than-0.074 mm (90wt percent) 2 Adding 1.5 percent of organic binder I (20 percent of biomass oil, 78 percent of sodium humate and 2 percent of glutamic acid) and 3 percent of water into the mixture, uniformly mixing the mixture, and performing forward and backward alternate ball milling by using a planetary ball mill, wherein the rotating speed of the planetary ball mill is 400r/min, the ball milling time is 30min, the mass percent of the obtained-200-mesh fraction is 100 percent, and the mass percent of the obtained-325-mesh fraction is not less thanAnd 84% of secondary mixture. Pelletizing the mixture by a disc pelletizer, wherein the rotating speed of the disc pelletizer is 30r/min, and organic binder II (15% of biomass oil, 78% of sodium humate, 2% of glutamic acid, 2% of glycine and FeCl) with the concentration of 15g/L is sprayed into the mixture in the pelletizing process 3 3%) so that the green pellets contained 8% of water. The yield of the green pellets was 95%. The green pellets are dried in an oven at 120 ℃ for 60min, the obtained dried pellets are vibrated for 300 times by a vibrating screen machine, and the size fraction below 0.05mm is only 2 percent after vibration. Roasting for 15min at 1000 ℃ to obtain the roasted pellet with the average strength of 1300N. The pellet meets the chlorination requirement of a boiling chlorination furnace.
In addition, the inorganic binder and the binder of the present invention have a significant effect on pellet grade.
Preparing small pellet material for boiling chlorination furnace with 100% high titanium slag and TiO thereof 2 The content was 87%. The better pelletizing effect can be obtained only by adopting about 5 percent of inorganic bentonite, and because the ash content of the inorganic bentonite reaches more than 80 percent, the TiO in the pellets is roasted for 20min at 1000 DEG C 2 The content of (D) is 83.8%; when the organic binder is adopted, the ash content of the organic binder is lower than 20%, organic matters are volatilized during combustion in the high-temperature roasting process, the addition amount of the organic binder is 2.5%, and TiO in finished pellets prepared by the organic binder is 2 The content of (A) is 86.4%, which is far higher than the pellet grade when inorganic bentonite is used.
In conclusion, the technical problem that the high-titanium slag is difficult to pelletize is solved by the method for preparing the small pellet material for the fluidized bed chlorination furnace from the full-high-titanium slag and combining the coal-based humic acid organic binder. The method can prepare high-strength green pellets, has high pelletizing rate and controllable pellet size, and has certain economic benefit.
Claims (8)
1. A method for preparing a small pellet material for a fluidized bed chlorination furnace from full-high titanium slag is characterized by comprising the following steps: mixing fine high-titanium slag, an organic binder I and water to obtain a mixture; after the mixture is finely ground, pelletizing, spraying an organic binder II solution into the mixture in the pelletizing process, and drying and roasting the obtained green pellets to obtain small pellet materials for the fluidized bed chlorination furnace;
The organic binder I comprises the following components in parts by mass:
5-30 parts of biomass oil;
65-90 parts of humic acid sodium;
1-5 parts of amino acid;
the organic binder II comprises biomass oil, sodium humate, amino acid and metal chloride salt with more than two valences in parts by mass as follows: 5-30 parts of biomass oil, 65-85 parts of humic acid sodium, 1-5 parts of amino acid and 1-5 parts of divalent or higher metal chloride.
2. The method for preparing the small pellet material for the boiling chlorination furnace by using the full-high titanium slag as claimed in claim 1, which is characterized in that:
the ash content of the sodium humate is not higher than 20%;
the biomass oil is pyrolysis oil of at least one biomass selected from corn, cotton, rape, wheat, rice plant straw, corncob, peanut shell and coconut shell;
the amino acid is glycine and/or glutamic acid.
3. The method for preparing the small pellet material for the boiling chlorination furnace by using the full-high titanium slag as claimed in claim 1, which is characterized in that: the addition amount of the organic binder I is 0.5-1.8% of the mass of the fine-grained high-titanium slag; the addition amount of the water accounts for 1-3% of the mass of the mixture.
4. The method for preparing the small pellet material for the boiling chlorination furnace by using the full-high titanium slag as claimed in claim 1 or 3, wherein the method comprises the following steps: the fine high-titanium slag meets the condition that the mass percentage of-200 meshes is not less than 80 percent, and the specific surface area is not less than 1650cm 2 /g。
5. The method for preparing the small pellet material for the boiling chlorination furnace by using the full-high titanium slag as claimed in claim 1, which is characterized in that:
the ash content of the sodium humate is not higher than 20%;
the biomass oil is pyrolysis oil of at least one biomass selected from corn, cotton, rape, wheat, rice plant straw, corncob, peanut shell and coconut shell;
the amino acid is glycine and/or glutamic acid;
the divalent or higher metal chloride salt comprises at least one of ferric chloride, calcium chloride, magnesium chloride and manganese chloride.
6. The method for preparing the small pellet material for the boiling chlorination furnace by using the full-high titanium slag as claimed in claim 1, which is characterized in that: the organic binder II is sprayed in the form of organic binder II solution with the concentration of 1 g/L-20 g/L, and the addition amount of the organic binder II is 6% -9% of the water content of the green pellets.
7. The method for preparing the small pellet material for the boiling chlorination furnace by using the full-high titanium slag as claimed in claim 1, which is characterized in that: the granularity of the fine grinding control mixture is 100 percent of-200 meshes, and not less than 75 percent of-325 meshes.
8. The method for preparing the small pellet material for the boiling chlorination furnace by using the full-high titanium slag as claimed in claim 1, which is characterized in that: the system of drying and roasting the green pellets is as follows: the drying temperature is 100-200 ℃, and the drying time is 30-60 min; the roasting temperature is 800-1000 ℃, and the roasting time is 10-30 min.
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| CN110809618A (en) * | 2016-05-13 | 2020-02-18 | 洛克沃国际公司 | Mineral wool binder |
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