CN113185159A - Efficient physical modification method for titanium gypsum - Google Patents
Efficient physical modification method for titanium gypsum Download PDFInfo
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- CN113185159A CN113185159A CN202110431339.7A CN202110431339A CN113185159A CN 113185159 A CN113185159 A CN 113185159A CN 202110431339 A CN202110431339 A CN 202110431339A CN 113185159 A CN113185159 A CN 113185159A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/002—Mixtures of different CaSO4-modifications, e.g. plaster of Paris and anhydrite, used as cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/007—After-treatment of the dehydration products, e.g. aging, stabilisation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
- C04B11/036—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the dry process, e.g. dehydrating in a fluidised bed or in a rotary kiln, i.e. to obtain beta-hemihydrate
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Abstract
The invention discloses a method for efficiently and physically modifying titanium gypsum, which comprises the following steps: drying the titanium gypsum; the titanium gypsum efficient physical modification method comprises the steps of adding a titanium gypsum homogenizing step in a preparation step of titanium gypsum physical modification, placing titanium gypsum powder in a kiln, keeping the temperature at 160-180 ℃, homogenizing the titanium gypsum powder for 2-3 hours, and homogenizing the titanium gypsum, wherein chemical components tend to be uniformly diffused and homogenized, and products of titanium gypsum calcination, namely beta hemihydrate gypsum, III type anhydrous gypsum and non-dehydrated dihydrate gypsum are uniformly distributed, so that the titanium gypsum powder is more uniform in texture, the thermal stability of titanium gypsum chips is remarkably enhanced, and the hardened strength of the titanium gypsum is improved.
Description
Technical Field
The invention relates to the technical field of titanium gypsum physical modification, in particular to a method for efficiently and physically modifying titanium gypsum.
Background
In the process of producing titanium dioxide by adopting a sulfuric acid method, lime is added to treat acid wastewater to neutralize a large amount of acid wastewater to produce industrial waste residue which takes dihydrate gypsum as a main component, in recent years, with the rapid temperature rise of the titanium industry, the construction of the titanium dioxide production line in China is rapidly developed, about 80 families of domestic titanium dioxide production enterprises are produced at present, more than 90 percent of titanium dioxide is produced by adopting a sulfuric acid method production process, and in 2011, the total output of titanium dioxide in China is 181.2 ten thousand tons. The annual emission of titanium gypsum is over 1000 ten thousand tons calculated according to the by-product of 6 tons of iron-containing gypsum per 1 ton of titanium dioxide.
At present, titanium gypsum is only used for according with cementitious material and additive in a small amount and used, a large amount of titanium gypsum is not effectively utilized, the plaster gypsum that discharges needs special a large amount of soil to stack, both waste arable land, there is the polluted environment, waste residue as refuse treatment piles in ground, receive the washing of rainwater, can lead to titanium gypsum to run off on the piling ground, titanium gypsum is through the washing away and soaking of rainwater simultaneously, soluble harmful position dissolves in water, through the flow and the circulation of water in the environment, can seriously pollute surface water and groundwater.
Disclosure of Invention
The invention aims to provide a method for efficiently and physically modifying titanium gypsum so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for efficiently and physically modifying titanium gypsum comprises the following steps:
s1: drying the titanium gypsum; drying titanium gypsum in a drying box to remove free water in the titanium gypsum, wherein the temperature of the drying box is 50-60 ℃, drying until the titanium gypsum is completely removed of the free water and is kept to constant weight, stopping drying, and taking the dried titanium gypsum out of the drying box.
S2: crushing titanium gypsum; and conveying the dried titanium gypsum into a ball mill through a charging vehicle, and then crushing the titanium gypsum through the ball mill to obtain titanium gypsum powder, wherein the fineness of the titanium gypsum powder is less than 15% of the surplus sieve passing through a 0.2mm square-hole sieve by mass percent.
S3: calcining titanium gypsum; inputting the crushed titanium gypsum powder into a kiln for calcination, wherein the calcination temperature of the titanium gypsum powder is 100-180 ℃, the calcination time of the titanium gypsum powder is 2-3 h, when the titanium gypsum powder is calcined, the product obtained after the titanium gypsum powder is calcined is a mixed phase which mainly contains beta hemihydrate gypsum and also contains III type anhydrous gypsum and non-dehydrated dihydrate gypsum, and when the content of the beta hemihydrate gypsum phase in the mixed phase is the highest, the strength of a sample after hydration and hardening reaches the maximum.
S4: homogenizing the titanium gypsum, placing the calcined titanium gypsum powder in a kiln, adjusting the temperature in the kiln to 160-180 ℃, and then firing the titanium gypsum powder for 5-8 hours through the kiln.
S5: and (3) aging the titanium gypsum, namely uniformly dispersing the titanium gypsum powder subjected to the homogenization treatment on the ground for aging treatment, wherein the aging treatment time of the titanium gypsum powder is 2d, and the aging temperature of the titanium gypsum powder is 10-25 ℃.
Preferably, the titanium gypsum comprises the main components of CaSO4 & 2H2O, the content of CaSO4 & 2H2O is 60% -80%, the main impurities of the titanium gypsum are Fe (OH)3, FeSO4 and Al (OH)3, and the crystal size of the titanium gypsum is small, the pH value of the titanium gypsum is 6-7, and the titanium gypsum is weakly acidic or neutral.
Preferably, the product of the calcined titanium gypsum powder is a mixed phase mainly comprising beta semi-hydrated gypsum and also comprising III type anhydrous gypsum and non-dehydrated dihydrate gypsum, wherein the beta semi-hydrated gypsum has a chemical formula of CaSO 4. 1/2H2O, and the III type anhydrous gypsum is a white crystal and is insoluble in water; the density of the type III anhydrous gypsum is 2.96, the melting point of the type III anhydrous gypsum is 1450 ℃, the gelling property of the type III anhydrous gypsum is poor, and the dehydrate gypsum without dehydration has no gelling property.
Preferably, the titanium gypsum is aged and also called blank storage, and the aim is to untwined titanium gypsum raw material particles, loose mud lumps, homogenize water, enable the water on the surfaces of the particles to permeate into the particles, enable the raw materials with uneven dryness and humidity or insufficient stirring to achieve uniform water through mutual permeation, and improve the physical properties of the raw materials.
Preferably, the three conditions of the titanium gypsum aging are granularity, time and temperature respectively, the finer the granularity of the titanium gypsum, the better the aging effect, and the shorter the aging time, the longer the aging time of the titanium gypsum, the better the effect, the better the plasticity of the aged titanium gypsum, easy molding, less cracks, low extrusion pressure, the improved green brick quality, difficult cracking and the like, and the correspondingly improved molding qualification rate
Preferably, the ball mill used for titanium gypsum grinding in step S2 is a tubular ball mill, which is widely used in the production industries of cement, silicate products, novel building materials, refractory materials, chemical fertilizers, metal ore dressing, glass ceramics and the like, and is used for dry or wet grinding treatment of various ores and other grindable materials, wherein the model of the tubular ball mill is MQG1870, the specification of the tubular ball mill is 1830 × 7000, the production capacity of the tubular ball mill is 6-7t/h, and the rotating speed is 23.91 r/min.
Preferably, the gypsum is homogenized in the step S4, the chemical components of the titanium gypsum powder tend to be uniformly diffused and homogenized when the titanium gypsum powder is kept in a high-temperature state in the kiln for a long time, and the beta hemihydrate gypsum, the III type anhydrite and the non-dehydrated dihydrate gypsum which are the products of calcining the titanium gypsum are uniformly distributed.
Preferably, the titanium gypsum calcination temperature in step S3 is 100-180 ℃, when the calcination is performed at 100-180 ℃, the strength of the sample after hydration hardening reaches the maximum when the beta hemihydrate gypsum phase content of the product after the titanium gypsum powder calcination is the highest, and when the calcination temperature is lower than or equal to 100-180 ℃, the beta hemihydrate gypsum phase content of the product after the titanium gypsum powder calcination decreases.
Compared with the prior art, the invention has the beneficial effects that: the titanium gypsum powder is placed in a kiln, the temperature is kept at 160-180 ℃, the titanium gypsum powder is homogenized for 2-3 h, chemical components of the titanium gypsum tend to be uniformly diffused and homogenized, and products beta semi-hydrated gypsum, III type anhydrous gypsum and dehydrate dihydrate gypsum calcined by the titanium gypsum are uniformly distributed, so that the titanium gypsum powder is more uniform in texture, the thermal stability of titanium gypsum scraps is remarkably enhanced, the hardened strength of the titanium gypsum is improved, the titanium gypsum homogenizing step is enhanced, the thermal stability of the titanium gypsum scraps is remarkably enhanced, the aging time of the titanium gypsum scraps is remarkably reduced, the physical modification method of the titanium gypsum is more efficient, and the working efficiency is improved.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a titanium gypsum high-efficiency physical modification method of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a method for efficiently and physically modifying titanium gypsum comprises the following steps:
s1: drying the titanium gypsum; drying titanium gypsum in a drying box to remove free water in the titanium gypsum, wherein the temperature of the drying box is 50-60 ℃, drying until the titanium gypsum is completely removed of the free water and is kept to constant weight, stopping drying, and taking the dried titanium gypsum out of the drying box.
S2: crushing titanium gypsum; and conveying the dried titanium gypsum into a ball mill through a charging vehicle, and then crushing the titanium gypsum through the ball mill to obtain titanium gypsum powder, wherein the fineness of the titanium gypsum powder is less than 15% of the surplus sieve passing through a 0.2mm square-hole sieve by mass percent.
S3: calcining titanium gypsum; inputting the crushed titanium gypsum powder into a kiln for calcination, wherein the calcination temperature of the titanium gypsum powder is 100-180 ℃, the calcination time of the titanium gypsum powder is 2-3 h, when the titanium gypsum powder is calcined, the product obtained after the titanium gypsum powder is calcined is a mixed phase which mainly contains beta hemihydrate gypsum and also contains III type anhydrous gypsum and non-dehydrated dihydrate gypsum, and when the content of the beta hemihydrate gypsum phase in the mixed phase is the highest, the strength of a sample after hydration and hardening reaches the maximum.
S4: homogenizing the titanium gypsum, placing the calcined titanium gypsum powder in a kiln, adjusting the temperature in the kiln to 160-180 ℃, and then firing the titanium gypsum powder for 5-8 hours through the kiln.
S5: and (3) aging the titanium gypsum, namely uniformly dispersing the titanium gypsum powder subjected to the homogenization treatment on the ground for aging treatment, wherein the aging treatment time of the titanium gypsum powder is 2d, and the aging temperature of the titanium gypsum powder is 10-25 ℃.
The product of titanium gypsum powder after calcination is a mixed phase which mainly contains beta semi-hydrated gypsum and also contains III type anhydrous gypsum and non-dehydrated dihydrate gypsum, the chemical formula of the beta semi-hydrated gypsum is CaSO 4. 1/2H2O, and the III type anhydrous gypsum of the beta semi-hydrated gypsum is a white crystal which is not dissolved in water; the density of the III type anhydrous gypsum is 2.96, the melting point of the III type anhydrous gypsum is 1450 ℃, the gelling property of the III type anhydrous gypsum is poor, the dehydrate dihydrate gypsum without gelling property is not available, the titanium gypsum is aged and also called blank storage, the aim is to loosen titanium gypsum raw material particles, loosen mud lumps, homogenize water, enable the water on the surfaces of the particles to permeate into the particles, enable the raw materials with uneven dryness and humidity or insufficient stirring to achieve uniform and consistent water through mutual permeation, improve the physical properties of the raw materials, the three conditions of titanium gypsum aging are respectively the particle size, the time and the temperature, the finer the particle size of the titanium gypsum, the better the aging effect, the shorter the aging time of the titanium gypsum, the better the aging effect, the better the plasticity, the easy molding, the less cracks and the low extrusion pressure of the titanium gypsum after aging, the quality of a brick blank is improved, the brick blank is not easy to crack and the like, and the molding qualification rate is correspondingly improved, the ball mill used for crushing the titanium gypsum in the step S2 is a tubular ball mill which is widely applied to the production industries of cement, silicate products, novel building materials, refractory materials, chemical fertilizers, metal mineral separation, glass ceramics and the like and carries out dry or wet crushing treatment on various ores and other grindable materials, wherein the model of the tubular ball mill is MQG1870, the specification of the tubular ball mill is 1830 x 7000, the production capacity of the tubular ball mill is 6-7t/h, the rotating speed is 23.91r/min, the gypsum is homogenized in the step S4, the chemical components of the titanium gypsum powder tend to be uniformly diffused and homogenized together under the condition of keeping a high temperature state in a kiln for a long time, the beta hemihydrate gypsum, the III anhydrous gypsum and the undehydrated dihydrate gypsum of the calcined titanium gypsum are uniformly distributed, the calcining temperature of the titanium gypsum in the step S3 is 100-180 ℃, and when the titanium gypsum is calcined at 100-180 ℃, when the content of the beta hemihydrate gypsum phase of the product of titanium gypsum powder after calcination is the highest, the strength of the sample after hydration and hardening reaches the maximum, and when the temperature is lower than or equal to 100-180 ℃, the content of the beta hemihydrate gypsum phase of the product of titanium gypsum powder after calcination is reduced.
The raw materials are more convenient to form after being aged (good plasticity, easy forming, few cracks, low extrusion pressure and the like), the quality of the green bricks is improved (the green bricks have smooth surfaces, good compactness, difficult cracking and the like), the forming qualification rate is correspondingly improved (the waste blank rate is low), the second function of aging is raw material storage, most areas of China have a rainy season every year, if no enough raw materials are available for production, serious loss is inevitably caused, and multiple pipes are needed, so that the materials are not only stored in a raw material yard, but also stored in the raw material aging process.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, 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. Without further limitation.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for efficiently and physically modifying titanium gypsum is characterized by comprising the following steps:
s1: drying the titanium gypsum; drying titanium gypsum in a drying box to remove free water in the titanium gypsum, wherein the temperature of the drying box is 50-60 ℃, drying until the titanium gypsum is completely removed of the free water and is kept to constant weight, stopping drying, and taking the dried titanium gypsum out of the drying box;
s2: crushing titanium gypsum; conveying the dried titanium gypsum into a ball mill through a charging vehicle, and then crushing the titanium gypsum through the ball mill to obtain titanium gypsum powder, wherein the fineness of the titanium gypsum powder is less than 15% of the surplus sieve of a 0.2mm square-hole sieve in percentage by mass;
s3: calcining titanium gypsum; inputting the crushed titanium gypsum powder into a kiln for calcination, wherein the calcination temperature of the titanium gypsum powder is 100-180 ℃, the calcination time of the titanium gypsum powder is 2-3 h, when the titanium gypsum powder is calcined, the calcined product of the titanium gypsum powder is a mixed phase which mainly contains beta hemihydrate gypsum and also contains III type anhydrous gypsum and dehydrate dihydrate gypsum, and when the content of the beta hemihydrate gypsum phase in the mixed phase is the highest, the strength of a sample after hydration and hardening reaches the maximum;
s4: homogenizing titanium gypsum, placing the calcined titanium gypsum powder in a kiln, adjusting the temperature in the kiln to 160-180 ℃, and then firing the titanium gypsum powder for 5-8 hours through the kiln;
s5: and (3) aging the titanium gypsum, namely uniformly dispersing the titanium gypsum powder subjected to the homogenization treatment on the ground for aging treatment, wherein the aging treatment time of the titanium gypsum powder is 2d, and the aging temperature of the titanium gypsum powder is 10-25 ℃.
2. The method for efficiently and physically modifying titanium gypsum according to claim 1, wherein the titanium gypsum comprises CaSO 4.2H 2O as a main component, and CaSO 4.2H2O is 60% -80%, the titanium gypsum comprises Fe (OH)3, FeSO4 and Al (OH)3 as main impurities, and the titanium gypsum has a pH value of 6-7 and is weakly acidic or neutral.
3. The method for high-efficiency physical modification of titanium gypsum according to claim 1, wherein the calcined product of titanium gypsum powder is a mixed phase mainly comprising beta hemihydrate gypsum and both type III anhydrite and anhydrite, wherein the beta hemihydrate gypsum has a chemical formula of CaSO 4-1/2H 2O, and the type III anhydrite is a white crystal and is insoluble in water; the density of the type III anhydrous gypsum is 2.96, the melting point of the type III anhydrous gypsum is 1450 ℃, the gelling property of the type III anhydrous gypsum is poor, the dehydrate gypsum without dehydration does not have the gelling property, and the calcining temperature has certain influence on the content of a calcined product during calcining treatment.
4. The method for efficient physical modification of titanium gypsum according to claim 1, wherein the titanium gypsum is aged, also called blank material, so as to loosen titanium gypsum raw material particles, loosen mud lumps, homogenize water, make water on the surface of particles penetrate into the particles, make the dry and wet raw materials uneven or insufficiently stirred and achieve uniform water through mutual penetration, and improve the physical properties of the raw materials.
5. The method for efficient physical modification of titanium gypsum according to claim 1, wherein the aging conditions of titanium gypsum are particle size, time and temperature, the finer the particle size of titanium gypsum, the better the aging effect, and the shorter the aging time, the longer the aging time of titanium gypsum, the better the aging effect, the better the plasticity of the aged titanium gypsum, easy molding, less cracks, low extrusion pressure, the improved quality of green brick, less cracking, and the like, and the improved molding yield.
6. The method for efficient physical modification of titanium gypsum as claimed in claim 1, wherein the ball mill used in step S2 is a tubular ball mill widely used in the industries of cement, silicate products, new building materials, refractory materials, fertilizers, metal ore dressing, glass ceramics and the like, and is used for dry or wet grinding of various ores and other grindable materials, wherein the model of the tubular ball mill is MQG1870, the specification of the tubular ball mill is 1830 × 7000, the production capacity of the tubular ball mill is 6-7t/h, and the rotation speed is 23.91 r/min.
7. The method for efficient physical modification of titanium gypsum according to claim 1, wherein in the step S4, the gypsum is homogenized, the chemical components of the titanium gypsum powder tend to be uniformly diffused and homogenized when the titanium gypsum powder is kept in a high temperature state in the kiln for a long time, and the beta hemihydrate gypsum, the type III anhydrite gypsum and the dehydrate dihydrate gypsum which are the products of calcination of the titanium gypsum are uniformly distributed.
8. The method for efficient physical modification of titanium gypsum according to claim 1, wherein the calcination temperature of titanium gypsum in step S3 is 100-180 ℃, when calcination is performed at 100-180 ℃, the strength of the sample after hydration hardening reaches the maximum when the beta hemihydrate gypsum phase content of the product of titanium gypsum powder calcination is the highest, and when the calcination temperature is lower than or equal to 100-180 ℃, the beta hemihydrate gypsum phase content of the product of titanium gypsum powder calcination decreases.
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