CN102002756B - Method of preparing calcium sulfate whisker by using sinter fume desulfurized by-products - Google Patents
Method of preparing calcium sulfate whisker by using sinter fume desulfurized by-products Download PDFInfo
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Abstract
The invention relates to a method of preparing calcium sulfate whiskers by using agglomerate fume desulfurized by-products. The method comprises the following steps: firstly, carry out size mixing: adding an oxidizer and an inhibitor to a suspension solution and reacting at 110 to 300 DEG C and 0.2 to 10 MPa; and then filtering, washing, drying and coating. The density of the prepared calcium sulfate whisker is from 2.0 to 2.3 g/cm<3>, the loose density is from 0.1 to 0.6 g/cm<3>, the length is from 10 to 300 mu m, the diameter is from 120 nm to 3 mu m, the melting point is from 1400 to 1500 DEG C, the tensile strength is from 14 to 20 GPa, the tensional modulus is from 150 to 180 GPa, the refractive index is from 1.3 to 1.6, and the water solubility (22 DEG C) is not more than 0.1%. Because the agglomerate fume desulfurized by-products are used as raw materials for preparing the calcium sulfate whiskers, the invention has the advantages that environment pollution caused by the agglomerate fume desulfurized by-products is reduced, and natural gypsum sources can be saved, thus providing a new way for high additional value utilization of the agglomerate fume desulfurized by-products.
Description
Technical field
The invention belongs to environmental technology field, relate to smoke gas treatment and solid waste disposal technology, be specifically related to utilize the agglomerate flue gas desulfurization byproduct to prepare the method for calcium sulfate crystal whiskers.
Background technology
Along with the lasting fast development of China's Iron And Steel Industry, the problem of environmental pollution that produces is very outstanding, especially " three wastes " discharging aspect enjoy the country show great attention to, in " the Iron And Steel Industry emission standard " of up-to-date revision with SO
2Emission control as one of important content, the mandatory regulation steel industry wants time limit to realize CER and flue gas qualified discharge.In Iron and Steel Enterprises in China, SO
2Quantity discharged is only second to the quantity discharged of power industry and Industrial Boiler, occupies the 3rd, and the SO of iron and steel enterprise's discharging
2In 50% ~ 70% from sintering circuit, adopt the semi-dry desulphurization technology to carry out sintering flue gas desulfurization, not only invest lowly, and desulfurization degree is higher, but in the semi-dry desulphurization process, produced a large amount of desulphurize fly ash, at present, only have the small part desulphurize fly ash to obtain utilizing both at home and abroad, and in some desulphurize fly ash, contain certain chlorion, make its application be subject to certain limitation, the overwhelming majority is abandoned, if rationally do not utilize, will cause secondary pollution and land occupation.
The agglomerate flue gas desulfurization byproduct is fine particulate, by mass percentage desulphurize fly ash main chemical compositions: CaO be 30%～33.5%, SiO
2Be 0.5%～4%, Al
2O
3Be 0.5%～3%, wherein the inferior sulfate radical in the calcium sulfite is with SO
2Count 20%～33%, Fe
2O
3Be 0.2%～1.5%, MgO is 0.5～1%, fugitive constituent 10%～20%, water content is 8%～15%.About 4～20 μ m of median size, color is from look or lime look, and wherein two water calcium sulfite content are the highest, generally all more than 60%, contain free-water generally 8%～15%, wherein also contain the impurity such as soluble salt that carbon ash, calcium carbonate, calcium sulfate and muriate form.
Reinforcement along with China environmental protection consciousness; the research of the comprehensive utilization aspect of agglomerate flue gas desulfurization byproduct receives people's concern gradually; and the utilization of agglomerate flue gas desulfurization byproduct can reduce fund, land occupation and the environmental pollution that consumes because stacking; reduce the consumption of the plaster of paris; and then the produced quantity of the minimizing plaster of paris, preserve the ecological environment.Therefore, many colleges and universities and enterprise have carried out a large amount of research to agglomerate flue gas desulfurization byproduct comprehensive utilization aspect, as utilize the agglomerate flue gas desulfurization byproduct to prepare sulfuric acid, cement setting retarder, gypsum building material etc.
Calcium sulfate crystal whiskers is under controllable condition, a kind of staple fibre that grows with the monocrystalline form, it has uniform cross section, complete profile and highly perfect internal structure, compare with glass fibre, advantage is that it has high intensity, trickle size, easilier be combined with organic high molecular compounds such as resin, rubber, plastics, and the visual appearance of product is good.Can be widely used in the numerous areas such as automobile, aerospace, chemical industry, metallurgy, national defence, machinery, electric, boats and ships, oil and building materials.
Summary of the invention
Problem for present agglomerate flue gas desulfurization byproduct utilization exists the invention provides a kind of method of utilizing the agglomerate flue gas desulfurization byproduct to prepare calcium sulfate crystal whiskers, reaches to alleviate solid waste to the pollution of environment and rationally utilize the purpose of desulfurizing byproduct.
The processing step of the inventive method is as follows:
(1) sizes mixing
In solid-liquid volume ratio 1:(4～20) ratio, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating the pH value is 2～10, stir, mixing speed is controlled to be 40 rev/mins～150 rev/mins, be that 110 ℃～300 ℃, pressure are under the condition of 0.2～10MPa in temperature, insulation 40min～500min carries out oxidizing reaction.
The oxygenant that adopts is oxygen, clorox, potassium hypochlorite, Potcrate, sodium chlorate, ammonium persulphate, Losantin or calcium chlorate; The inhibitor that adopts is sodium phosphate, nitric acid, trimagnesium phosphate, magnesium chloride, phosphoric acid or sulfuric acid, and wherein the mass concentration of nitric acid is 0.05% ~ 3%, and the mass concentration of sulfuric acid is 0.05% ~ 3%; By mass percentage, the add-on of oxygenant is 0.5%～10% of suspension quality, and the consumption of inhibitor is 0.5%～10% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out vacuum suction filter, centrifuging or filter press, wash filter cake with water.
(4) drying
Be dry under 80 ℃～600 ℃ the condition in temperature with the material after the washing, insulation 10min～120min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 1 ~ 10 minute after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts vacuum suction filter, centrifuging or filter press; Drying temperature is under 80 ℃～600 ℃ the condition, time 10min～120min.
Finishing agent is the ethanolic soln of stearic acid, titanic acid ester, tetraethoxy, polyvinyl alcohol or phosphoric acid ester, the mass concentration of solution is 1% ~ 5%, the finishing agent consumption is 0.5% ~ 5% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of the inventive method preparation is 2.2～3.2g/cm
3, aerated density is 0.1～0.6 g/cm
3, length is 10 μ m～300 μ m, and diameter is 120nm～3 μ m, and fusing point is 1400 ~ 1500 ℃, and tensile strength is 14 ~ 20GPa, and tensile modulus is 150 ~ 180GPa, and refractive index is 1.3 ~ 1.6, water-soluble (22 ℃)≤0.1%.
Prepare calcium sulfate crystal whiskers take the agglomerate flue gas desulfurization byproduct as raw material and not only can reduce flue gas desulfurization byproducts for sintered pellets to the pollution of environment, can also save plaster of paris resource, and open up new way for the high value added utilization of agglomerate flue gas desulfurization byproduct.The inventive method utilizes the agglomerate flue gas desulfurization byproduct to be raw material, effectively alleviates the problem that the agglomerate flue gas desulfurization byproduct dyes environment; Adopt Direct Hydrothermal oxidation-crystallization process to prepare calcium sulfate crystal whiskers, not only technical process is short, and production cost is low.
Description of drawings
Accompanying drawing is process flow diagram of the present invention.
Embodiment
The agglomerate flue gas desulfurization byproduct that embodiment adopts is fine particulate, by mass percentage desulphurize fly ash main chemical compositions: CaO be 30%～33.5%, SiO
2Be 0.5%～4%, Al
2O
3Be 0.5%～3%, wherein the inferior sulfate radical in the calcium sulfite is with SO
2Count 20%～33%, Fe
2O
3Be 0.2%～1.5%, MgO is 0.5～1%, fugitive constituent 10%～20%, water content is 8%～15%.Median size 4～20 μ m.
Embodiment 1
It is as follows to utilize the agglomerate flue gas desulfurization byproduct to prepare the method processing step of calcium sulfate crystal whiskers:
(1) sizes mixing
In the ratio of solid-liquid volume ratio 1:12, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 6, stirs, and mixing speed is controlled to be 95 rev/mins, is that 200 ℃, pressure are under the condition of 5MPa in temperature, is incubated 270min, carries out oxidizing reaction.
The oxygenant that adopts is oxygen; The inhibitor that adopts is sodium phosphate; By mass percentage, the add-on of oxygenant is 5% of suspension quality, and the consumption of inhibitor is 5% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out vacuum suction filter, wash filter cake with water.
(4) drying
Be dry under 340 ℃ the condition in temperature with the material after the washing, insulation 65min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 5 minutes after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts vacuum suction filter; Drying temperature is under 340 ℃ the condition, time 65min.
Finishing agent is stearic ethanolic soln, the mass concentration of solution is 3%, the finishing agent consumption is 2.6% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of preparation is 2.7g/cm
3, aerated density is 0.35g/cm
3, length is 150 μ m, and diameter is 6000nm, and fusing point is 1450 ℃, and tensile strength is 16GPa, and tensile modulus is 175GPa, and refractive index is 1.4, water-soluble (22 ℃)≤0.1%.
Embodiment 2
It is as follows to utilize the agglomerate flue gas desulfurization byproduct to prepare the method processing step of calcium sulfate crystal whiskers:
(1) sizes mixing
In the ratio of solid-liquid volume ratio 1:20, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 10, stirs, and mixing speed is controlled to be 150 rev/mins, is that 300 ℃, pressure are under the condition of 10MPa in temperature, is incubated 40min, carries out oxidizing reaction.
The oxygenant that adopts is clorox; The inhibitor that adopts is nitric acid, and the mass concentration of nitric acid is 1.5%; By mass percentage, the add-on of oxygenant is 10% of suspension quality, and the consumption of inhibitor is 10% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out centrifuging, wash filter cake with water.
(4) drying
Be dry under 600 ℃ the condition in temperature with the material after the washing, insulation 10min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 10 minutes after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts centrifuging; Drying temperature is under 600 ℃ the condition, time 10min.
Finishing agent is the ethanolic soln of titanic acid ester (tetrabutyl titanate or titanium isopropylate), the mass concentration of solution is 5%, the finishing agent consumption is 5% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of preparation is 3.2g/cm
3, aerated density is 0.6 g/cm
3, length is 10 μ m μ m, and diameter is 120nm, and fusing point is 1500 ℃, and tensile strength is 20GPa, and tensile modulus is 150GPa, and refractive index is 1.3, water-soluble (22 ℃)≤0.1%.
Embodiment 3
It is as follows to utilize the agglomerate flue gas desulfurization byproduct to prepare the method processing step of calcium sulfate crystal whiskers:
(1) sizes mixing
In the ratio of solid-liquid volume ratio 1:4, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 2, stirs, and mixing speed is controlled to be 40 rev/mins, is that 110 ℃, pressure are under the condition of 0.2MPa in temperature, is incubated 500min, carries out oxidizing reaction.
The oxygenant that adopts is potassium hypochlorite; The inhibitor that adopts is trimagnesium phosphate; By mass percentage, the add-on of oxygenant is 0.5% of suspension quality, and the consumption of inhibitor is 0.5% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out filter press, wash filter cake with water.
(4) drying
Be dry under 80 ℃ the condition in temperature with the material after the washing, insulation 120min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 1 minute after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts filter press; Drying temperature is under 80 ℃ the condition, time 120min.
Finishing agent is the ethanolic soln of tetraethoxy, the mass concentration of solution is 1%, the finishing agent consumption is 0.5% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of preparation is 2.2g/cm
3, aerated density is 0.1 g/cm
3, length is 300 μ m, and diameter is 3 μ m, and fusing point is 1400 ℃, and tensile strength is 14GPa, and tensile modulus is 180GPa, and refractive index is 1.6, water-soluble (22 ℃)≤0.1%.
Embodiment 4
It is as follows to utilize the agglomerate flue gas desulfurization byproduct to prepare the method processing step of calcium sulfate crystal whiskers:
(1) sizes mixing
In the ratio of solid-liquid volume ratio 1:8, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 7, stirs, and mixing speed is controlled to be 100 rev/mins, is that 150 ℃, pressure are under the condition of 2.5MPa in temperature, is incubated 300min, carries out oxidizing reaction.
The oxygenant that adopts is Potcrate; The inhibitor that adopts is magnesium chloride; By mass percentage, the add-on of oxygenant is 3% of suspension quality, and the consumption of inhibitor is 3% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out vacuum suction filter, wash filter cake with water.
(4) drying
Be dry under 200 ℃ the condition in temperature with the material after the washing, insulation 80min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 8 minutes after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts vacuum suction filter; Drying temperature is under 200 ℃ the condition, time 80min.
Finishing agent is the ethanolic soln of polyvinyl alcohol (PVA05-88, PVAl7-88 or PVA-124), the mass concentration of solution is 2%, the finishing agent consumption is 1.5% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of preparation is 2.6g/cm
3, aerated density is 0.5g/cm
3, length is 195 μ m, and diameter is 2 μ m, and fusing point is 1490 ℃, and tensile strength is 19GPa, and tensile modulus is 158GPa, and refractive index is 1.5, water-soluble (22 ℃)≤0.1%.
Embodiment 5
It is as follows to utilize the agglomerate flue gas desulfurization byproduct to prepare the method processing step of calcium sulfate crystal whiskers:
(1) sizes mixing
In the ratio of solid-liquid volume ratio 1:15, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 5, stirs, and mixing speed is controlled to be 60 rev/mins, is that 260 ℃, pressure are under the condition of 7.5MPa in temperature, is incubated 60min, carries out oxidizing reaction.
The oxygenant that adopts is sodium chlorate; The inhibitor that adopts is phosphoric acid; By mass percentage, the add-on of oxygenant is 4.5% of suspension quality, and the consumption of inhibitor is 4.5% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out centrifuging, wash filter cake with water.
(4) drying
Be dry under 500 ℃ the condition in temperature with the material after the washing, insulation 20min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 9 minutes after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts centrifuging; Drying temperature is under 500 ℃ the condition, time 20min.
Finishing agent is the ethanolic soln of phosphoric acid ester (LYCO-P08 or LYCO-P30), the mass concentration of solution is 2%, the finishing agent consumption is 2% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of preparation is 3.1g/cm
3, aerated density is 0.2g/cm
3, length is 50 μ m, and diameter is 220nm, and fusing point is 1420 ℃, and tensile strength is 15GPa, and tensile modulus is 160GPa, and refractive index is 1.5, water-soluble (22 ℃)≤0.1%.
Embodiment 6
It is as follows to utilize the agglomerate flue gas desulfurization byproduct to prepare the method processing step of calcium sulfate crystal whiskers:
(1) sizes mixing
In the ratio of solid-liquid volume ratio 1:6, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 4, stirs, and mixing speed is controlled to be 50 rev/mins, is that 280 ℃, pressure are under the condition of 8.5MPa in temperature, is incubated 65min, carries out oxidizing reaction.
The oxygenant that adopts is ammonium persulphate; The inhibitor that adopts is sulfuric acid, and the mass concentration of sulfuric acid is 1.5%; By mass percentage, the add-on of oxygenant is 7% of suspension quality, and the consumption of inhibitor is 7% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out filter press, wash filter cake with water.
(4) drying
Be dry under 350 ℃ the condition in temperature with the material after the washing, insulation 100min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 6 minutes after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts filter press; Drying temperature is under 350 ℃ the condition, time 90min.
Finishing agent is stearic ethanolic soln, the mass concentration of solution is 4%, the finishing agent consumption is 4% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of preparation is 2.7g/cm
3, aerated density is 0.2g/cm
3, length is 170 μ m, and diameter is 1.2 μ m, and fusing point is 1490 ℃, and tensile strength is 19GPa, and tensile modulus is 170GPa, and refractive index is 1.6, water-soluble (22 ℃)≤0.1%.
Embodiment 7
It is as follows to utilize the agglomerate flue gas desulfurization byproduct to prepare the method processing step of calcium sulfate crystal whiskers:
(1) sizes mixing
In the ratio of solid-liquid volume ratio 1:10, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 3, stirs, and mixing speed is controlled to be 130 rev/mins, is that 190 ℃, pressure are under the condition of 4.8MPa in temperature, is incubated 130min, carries out oxidizing reaction.
The oxygenant that adopts is Losantin; The inhibitor that adopts is sulfuric acid, and h 2 so 4 concentration is 3%; By mass percentage, the add-on of oxygenant is 6% of suspension quality, and the consumption of inhibitor is 6% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out vacuum suction filter, wash filter cake with water.
(4) drying
Be dry under 400 ℃ the condition in temperature with the material after the washing, insulation 70min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 6 minutes after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts vacuum suction filter; Drying temperature is under 400 ℃ the condition, time 70min.
Finishing agent is the ethanolic soln of tetraethoxy, the mass concentration of solution is 4%, the finishing agent consumption is 2% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of preparation is 3.2g/cm
3, aerated density is 0.19g/cm
3, length is 120 μ m, and diameter is 520nm, and fusing point is 1410 ℃, and tensile strength is 20GPa, and tensile modulus is 180GPa, and refractive index is 1.3, water-soluble (22 ℃)≤0.1%.
Embodiment 8
It is as follows to utilize the agglomerate flue gas desulfurization byproduct to prepare the method processing step of calcium sulfate crystal whiskers:
(1) sizes mixing
In the ratio of solid-liquid volume ratio 1:6, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension.
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 9, stirs, and mixing speed is controlled to be 150 rev/mins, is that 220 ℃, pressure are under the condition of 6MPa in temperature, is incubated 200min, carries out oxidizing reaction.
The oxygenant that adopts is calcium chlorate; The inhibitor that adopts is nitric acid, and the mass concentration of nitric acid is 3%; By mass percentage, the add-on of oxygenant is 2% of suspension quality, and the consumption of inhibitor is 2% of suspension quality.
(3) filter and wash
Material behind the high temperature oxidation is carried out filter press, wash filter cake with water.
(4) drying
Be dry under 320 ℃ the condition in temperature with the material after the washing, insulation 30min obtains unmodified calcium sulfate crystal whiskers.
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 3 minutes after, filter, drying, obtain the calcium sulfate crystal whiskers product.Filter the method that adopts filter press; Drying temperature is under 320 ℃ the condition, time 30min.
Finishing agent is the ethanolic soln of tetraethoxy, the mass concentration of solution is 5%, the finishing agent consumption is 1.5% of unmodified calcium sulfate crystal whiskers quality, the final calcium sulfate crystal whiskers product that obtains modification, the organic high molecular compounds such as calcium sulfate crystal whiskers product and resin, rubber, plastics have good consistency after the modification.
The calcium sulfate crystal whiskers density of preparation is 2.4g/cm
3, aerated density is 0.5 g/cm
3, length is 60 μ m, and diameter is 1280nm, and fusing point is 1478 ℃, and tensile strength is 19GPa, and tensile modulus is 180GPa, and refractive index is 1.6, water-soluble (22 ℃)≤0.1%.
Claims (3)
1. method of utilizing the agglomerate flue gas desulfurization byproduct to prepare calcium sulfate crystal whiskers is characterized in that processing step is as follows:
(1) sizes mixing
In solid-liquid volume ratio 1:(4～20) ratio, the agglomerate flue gas desulfurization byproduct is mixed with water, obtain suspension;
(2) high temperature oxidation
Add oxygenant and inhibitor in the suspension that makes to step (1), regulating pH value is 2～10, stir, and be that 110 ℃～300 ℃, pressure are under the condition of 0.2～10MPa in temperature, be incubated 40min～500min, carry out oxidizing reaction;
The oxygenant that adopts is oxygen, clorox, potassium hypochlorite, Potcrate, sodium chlorate, ammonium persulphate, Losantin or calcium chlorate; The inhibitor that adopts is sodium phosphate, nitric acid, trimagnesium phosphate, magnesium chloride, phosphoric acid or sulfuric acid, and wherein the mass concentration of nitric acid is 0.05% ~ 3%, and the mass concentration of sulfuric acid is 0.05% ~ 3%; By mass percentage, the add-on of oxygenant is 0.5%～10% of suspension quality, and the consumption of inhibitor is 0.5%～10% of suspension quality;
(3) filter and wash
Material behind the high temperature oxidation is carried out vacuum suction filter, centrifuging or filter press, wash filter cake with water;
(4) drying
Be dry under 80 ℃～600 ℃ the condition in temperature with the material after the washing, insulation 10min～120min obtains unmodified calcium sulfate crystal whiskers;
(5) cover with paint, lacquer, colour wash, etc.
In unmodified calcium sulfate crystal whiskers, add finishing agent, react at normal temperatures 1 ~ 10 minute after, filter, drying, obtain the calcium sulfate crystal whiskers product, filter the method that adopts vacuum suction filter, centrifuging or filter press; Drying temperature is under 80 ℃～600 ℃ the condition, time 10min～120min;
Finishing agent is the ethanolic soln of stearic acid, titanic acid ester, tetraethoxy, polyvinyl alcohol or phosphoric acid ester, and the mass concentration of solution is 1% ~ 5%, and the finishing agent consumption is 0.5% ~ 5% of unmodified calcium sulfate crystal whiskers quality.
2. according to the method for utilizing the agglomerate flue gas desulfurization byproduct to prepare calcium sulfate crystal whiskers claimed in claim 1, it is characterized in that in the step (2) that mixing speed is controlled to be 40 rev/mins～150 rev/mins.
3. according to the method for utilizing the agglomerate flue gas desulfurization byproduct to prepare calcium sulfate crystal whiskers claimed in claim 1, it is characterized in that the calcium sulfate crystal whiskers density for preparing is 2.2～3.2g/cm
3, aerated density is 0.1～0.6 g/cm
3, length is 10 μ m～300 μ m, and diameter is 120nm～3 μ m, and fusing point is 1400 ~ 1500 ℃, and tensile strength is 14 ~ 20GPa, and tensile modulus is 150 ~ 180GPa, and refractive index is 1.3 ~ 1.6,22 ℃ of water-soluble≤0.1%.
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| CN107400929B (en) * | 2017-03-03 | 2019-07-09 | 安徽工业大学 | A method of the sintering flue gas semi-dry desulphurization ash based on acid oxidation prepares calcium sulfate crystal whiskers |
| CN107758675B (en) * | 2017-11-01 | 2020-07-31 | 昆明理工大学 | Method for preparing silica gel and calcium sulfate whiskers from yellow phosphorus furnace slag |
| CN108950674B (en) * | 2018-07-24 | 2021-08-13 | 北京科技大学 | Method for preparing semi-hydrated and anhydrous calcium sulfate whiskers by one step through hydrothermal method |
| CN109082709B (en) * | 2018-08-31 | 2020-08-28 | 安徽工业大学 | Method for synthesizing calcium sulfate whiskers by using sintered flue gas desulfurization ash through one-step method |
| CN110541188B (en) * | 2019-10-18 | 2021-02-05 | 郑州中科新兴产业技术研究院 | Method for preparing calcium sulfate hemihydrate crystal whisker with high length-diameter ratio by using calcium sulfate dihydrate |
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