CN104176955A - Modification method for fluorgypsum - Google Patents
Modification method for fluorgypsum Download PDFInfo
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- CN104176955A CN104176955A CN201410390525.0A CN201410390525A CN104176955A CN 104176955 A CN104176955 A CN 104176955A CN 201410390525 A CN201410390525 A CN 201410390525A CN 104176955 A CN104176955 A CN 104176955A
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Abstract
The invention discloses a modification method for fluorgypsum. Grinding, smashing, heat treatment, primary chemical modification, secondary chemical modification and calcinations are adopted; heat treatment is carried out for 5-8 hours at the temperature of 105-115 DEG C; during primary chemical modification, 1-1.8 parts by weight of calcium hydroxide, 1-2 parts by weight of blast furnace slag, 1-1.5 parts by weight of alum calcined in the step one and 0.5-0.8 part by weight of dolomite calcined in the step two are added into every 100 parts by weight of the fluorgypsum subjected to heat treatment; during secondary chemical modification, 0.5-0.8 part by weight of coal ash, 0.5-0.8 part by weight of modified corn straw fibers and 1-1.2 parts by weight of bentonite are added into every 100 parts by weight of calcined fluorgypsum, wherein the modified corn straw fibers are styrene-acrylic emulsion modified corn straw fibers. The modification method for fluorgypsum has the advantages that condensation time of the modified fluorgypsum is shortened, and mechanical strength of the modified fluorgypsum is improved.
Description
Technical field
The present invention relates to fluorgypsum technical field, relate in particular to a kind of method of modifying of fluorgypsum.
Background technology
Fluorgypsum is the main byproduct in hydrofluoric acid and sodium fluoroaluminate production process, mainly originates from inorganic fluoride and organic fluoride factory and other Acid of Hydrofluoric Acid Production factory.Every production 1t hydrofluoric acid generates the anhydrous fluorgypsum of about 3.6t.The main component of fluorgypsum is calcium sulfate, and contains partially fluorinated calcium and other fluorochemicals, and H sometimes
2sO
4content is very high, makes the fluorgypsum of discharging be acid, belongs to severe corrosive poisonous and harmful refuse, and the fluorgypsum that does not add processing can not directly be put and abandon, and is also difficult to be utilized.Because fluorgypsum solubleness is lower and dissolution rate is slow, time of coagulation is very long again, and hydration and hardening body intensity is very little, these drawbacks limit its application.At present, except part fluorgypsum is utilized, most of as general solid waste, stored up, land occupation not only, objectionable impurities wherein also can produce and pollute water body simultaneously, and physical environment is produced and threatened.Therefore, how to solve the especially historical wet fluorgypsum problem of storing up of fluorgypsum, it is turned waste into wealth, the comprehensive utilization that realizes gypsum resource is a very urgent problem.
Summary of the invention
The present invention proposes a kind of method of modifying of fluorgypsum, by the fluorgypsum after the method modification, time of coagulation is short, and hydration and hardening intensity is high.
The method of modifying that the present invention proposes a kind of fluorgypsum, comprises the following steps:
S1, fluorgypsum is put into grinding in ball grinder pulverize, put into baking oven and heat-treat after sieving, thermal treatment temp is 105-115 ℃, and the time is 5-8h;
S2, alum is put into retort furnace calcine, calcining temperature is 600-650 ℃, and calcination time is 0.8-1.3h, be cooled to after room temperature grind, sieving for standby; Rhombspar is put into retort furnace and calcine, calcining temperature is 700-800 ℃, and calcination time is 1-1.5h, be cooled to after room temperature grind, sieving for standby;
In S3, the fluorgypsum in S1 after thermal treatment, add in calcium hydroxide, blast-furnace slag, S2 the rhombspar after calcining in alum after calcining, S2, stir, standing 10-20h carries out chemical modification one time, and then 250-300 ℃ of calcining, calcination time is 0.5-1.5h; Wherein, add by weight in 1-1.8 part calcium hydroxide, 1-2 part blast-furnace slag, 1-1.5 part S1 the rhombspar after calcining in the alum after calcining, 0.5-0.8 part S2 in the fluorgypsum after every 100 parts of thermal treatments;
In S4, the fluorgypsum in S3 after calcining, add flyash, corn straw modification fiber, wilkinite to carry out secondary chemical modification; Wherein, in the fluorgypsum after every 100 parts of calcinings, add 0.5-0.8 part flyash, 0.5-0.8 part corn straw modification fiber, 1-1.2 part wilkinite by weight; Described corn straw modification fiber is Modification of Styrene-Acrylate Emulsion corn stalk fiber;
S5, the fluorgypsum obtaining is put into curing field maintenance 10 days appear on the scene afterwards in S4.
Preferably, in S1, thermal treatment temp is 110-113 ℃, and the time is 6-7h.
Preferably, in S1, thermal treatment temp is 112 ℃, and the time is 6.3h.
Preferably, in S3, the fluorgypsum in S1 after thermal treatment carries out after a chemical modification, and 285-295 ℃ of calcining, calcination time is 0.8-1.2h.
Preferably, in S3, the fluorgypsum in S1 after thermal treatment carries out after a chemical modification, and 290 ℃ of calcinings, calcination time is 1.0h.
Preferably, in S3, in a chemical modification, in the fluorgypsum after every 100 parts of thermal treatments, add by weight in 1.2-1.6 part calcium hydroxide, 1.5-1.7 part blast-furnace slag, 1.2-1.3 part S2 the rhombspar after calcining in alum after calcining, 0.6-0.65 part S2.
Preferably, in S3, in a chemical modification, in the fluorgypsum after every 100 parts of thermal treatments, add by weight in 1.4 parts of calcium hydroxides, 1.6 parts of blast-furnace slags, 1.25 parts of S2 the rhombspar after calcining in the alum after calcining, 0.63 part of S2.
Preferably, in S4, in secondary chemical modification, in the fluorgypsum after every 100 parts of calcinings, add by weight 0.6-0.68 part flyash, 0.6-0.7 part corn straw modification fiber, 1.1-1.15 part wilkinite.
Preferably, in S4, in secondary chemical modification, in the fluorgypsum after every 100 parts of calcinings, add by weight 0.65 part of flyash, 0.68 part of corn straw modification fiber, 1.13 parts of wilkinites.
In the method for modifying of fluorgypsum of the present invention, adopted and ground and thermal treatment, change, destroyed the crystal lattice of fluorgypsum after modification, increase its lattice distortion and defect, increase the irregularity of its specific surface area and surface tissue, improve the hydration activity of fluorgypsum after modification, promoted the hardening of fluorgypsum after modification; Adopted chemical modifying process twice, in a chemical modification, added alum after calcining and the rhombspar after calcining, made the fluorgypsum after modification, dihydrate gypsum crystal quantity increases, and crystal development is complete, length-to-diameter ratio increases, and is needle-like more, has reduced obvious bulk or granular crystal, between crystal, overlap joint is fine and close, has improved the hydration and hardening intensity of fluorgypsum after modification; In secondary chemical modification, added Modification of Styrene-Acrylate Emulsion corn stalk fiber, the existence of benzene emulsion, on the one hand, the surface of the original rough porous of corn stalk fiber is filled, improve effective contact area of corn stalk fiber and fluorgypsum matrix, improved the interface bond strength of corn stalk fiber and fluorgypsum matrix; On the other hand, make the junction, interface of corn stalk fiber and fluorgypsum matrix form a flexible interface, when the micro-crack extension of fluorgypsum matrix carry load generation arrives this interfacial layer, its propagation rate can slow down because of the existence of flexible interface layer, alleviate the stress concentration that material sudden change causes, improved the bending and compressive strength of modification fluorgypsum.
In the method for modifying of fluorgypsum of the present invention, optimize the modified technique of fluorgypsum, selected suitable properties-correcting agent, controlled the content of each composition in properties-correcting agent, adopted the fluorgypsum of the method modification, time of coagulation is short, after hydration and hardening, mechanical strength is high, and fluorgypsum is turned waste into wealth.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail; should understand; embodiment is only for the present invention is described, rather than for the present invention is limited, and any modification of making on basis of the present invention, is equal to replacement etc. all in protection scope of the present invention.
Embodiment 1
The method of modifying of fluorgypsum of the present invention, comprises the following steps:
S1, fluorgypsum is put into grinding in ball grinder pulverize, cross and put into baking oven after 80 mesh sieves and heat-treat, thermal treatment temp is 105 ℃, and the time is 8h;
S2, alum is put into retort furnace calcine, calcining temperature is 650 ℃, and calcination time is 0.8h, be cooled to after room temperature grind, to cross 100 mesh sieves standby; Rhombspar is put into retort furnace and calcine, calcining temperature is 800 ℃, and calcination time is 1h, be cooled to after room temperature grind, to cross 100 mesh sieves standby;
In S3, the fluorgypsum in S1 after thermal treatment, add in calcium hydroxide, blast-furnace slag, S2 the rhombspar after calcining in alum after calcining, S2, stir, standing 20h carries out chemical modification one time, and then 268 ℃ of calcinings, calcination time is 1.3h; Wherein, the calcium hydroxide adding in the fluorgypsum after every 100 parts of thermal treatments is by weight that 1.4 parts, blast-furnace slag are that in 1 part, S2, the alum after calcining is that in 1 part, S2, the rhombspar after calcining is 0.8 part;
In S4, the fluorgypsum in S3 after calcining, add flyash, corn straw modification fiber, wilkinite to carry out secondary chemical modification; Wherein, the flyash adding in the fluorgypsum after every 100 parts of calcinings is by weight that 0.6 part, corn straw modification fiber are that 0.5 part, wilkinite are 1 part; Described corn straw modification fiber is Modification of Styrene-Acrylate Emulsion corn stalk fiber;
S5, the fluorgypsum obtaining is put into curing field maintenance 10 days appear on the scene afterwards in S4.
Embodiment 2
The method of modifying of fluorgypsum of the present invention, comprises the following steps:
S1, fluorgypsum is put into grinding in ball grinder pulverize, cross and put into baking oven after 100 mesh sieves and heat-treat, thermal treatment temp is 115 ℃, and the time is 5h;
S2, alum is put into retort furnace calcine, calcining temperature is 600 ℃, and calcination time is 1.3h, be cooled to after room temperature grind, to cross 100 mesh sieves standby; Rhombspar is put into retort furnace and calcine, calcining temperature is 722 ℃, and calcination time is 1.38h, be cooled to after room temperature grind, to cross 100 mesh sieves standby;
In S3, the fluorgypsum in S1 after thermal treatment, add in calcium hydroxide, blast-furnace slag, S2 the rhombspar after calcining in alum after calcining, S2, stir, standing 10h carries out chemical modification one time, and then 250 ℃ of calcinings, calcination time is 1.5h; Wherein, the calcium hydroxide adding in the fluorgypsum after every 100 parts of thermal treatments is by weight that 1 part, blast-furnace slag are that in 2 parts, S2, the alum after calcining is that in 1.3 parts, S2, the rhombspar after calcining is 0.5 part;
In S4, the fluorgypsum in S3 after calcining, add flyash, corn straw modification fiber, wilkinite to carry out secondary chemical modification; Wherein, the flyash adding in the fluorgypsum after every 100 parts of calcinings is by weight that 0.8 part, corn straw modification fiber are that 0.8 part, wilkinite are 1.1 parts; Described corn straw modification fiber is Modification of Styrene-Acrylate Emulsion corn stalk fiber;
S5, the fluorgypsum obtaining is put into curing field maintenance 10 days appear on the scene afterwards in S4.
Embodiment 3
The method of modifying of fluorgypsum of the present invention, comprises the following steps:
S1, fluorgypsum is put into grinding in ball grinder pulverize, put into baking oven and heat-treat after sieving, thermal treatment temp is 108 ℃, and the time is 6.3h;
S2, alum is put into retort furnace calcine, calcining temperature is 621 ℃, and calcination time is 0.95h, be cooled to after room temperature grind, sieving for standby; Rhombspar is put into retort furnace and calcine, calcining temperature is 700 ℃, and calcination time is 1.5h, be cooled to after room temperature grind, sieving for standby;
In S3, the fluorgypsum in S1 after thermal treatment, add in calcium hydroxide, blast-furnace slag, S2 the rhombspar after calcining in alum after calcining, S2, stir, standing 14h carries out chemical modification one time, and then 300 ℃ of calcinings, calcination time is 0.5h; Wherein, the calcium hydroxide adding in the fluorgypsum after every 100 parts of thermal treatments is by weight that 1.8 parts, blast-furnace slag are that in 1.3 parts, S2, the alum after calcining is that in 1.5 parts, S2, the rhombspar after calcining is 0.6 part;
In S4, the fluorgypsum in S3 after calcining, add flyash, corn straw modification fiber, wilkinite to carry out secondary chemical modification; Wherein, the flyash adding in the fluorgypsum after every 100 parts of calcinings is by weight that 0.5 part, corn straw modification fiber are that 0.7 part, wilkinite are 1.2 parts; Described corn straw modification fiber is Modification of Styrene-Acrylate Emulsion corn stalk fiber;
S5, the fluorgypsum obtaining is put into curing field maintenance 10 days appear on the scene afterwards in S4.
Embodiment 4
The method of modifying of fluorgypsum of the present invention, comprises the following steps:
S1, fluorgypsum is put into grinding in ball grinder pulverize, put into baking oven and heat-treat after sieving, thermal treatment temp is 112 ℃, and the time is 6.3h;
S2, alum is put into retort furnace calcine, calcining temperature is 640 ℃, and calcination time is 1.05h, be cooled to after room temperature grind, sieving for standby; Rhombspar is put into retort furnace and calcine, calcining temperature is 750 ℃, and calcination time is 1.3h, be cooled to after room temperature grind, sieving for standby;
In S3, the fluorgypsum in S1 after thermal treatment, add in calcium hydroxide, blast-furnace slag, S2 the rhombspar after calcining in alum after calcining, S2, stir, standing 16h carries out chemical modification one time, and then 290 ℃ of calcinings, calcination time is 1.0h; Wherein, the calcium hydroxide adding in the fluorgypsum after every 100 parts of thermal treatments is by weight that 1.4 parts, blast-furnace slag are that in 1.6 parts, S2, the alum after calcining is that in 1.25 parts, S2, the rhombspar after calcining is 0.63 part;
In S4, the fluorgypsum in S3 after calcining, add flyash, corn straw modification fiber, wilkinite to carry out secondary chemical modification; Wherein, the flyash adding in the fluorgypsum after every 100 parts of calcinings is by weight that 0.65 part, corn straw modification fiber are that 0.68 part, wilkinite are 1.13 parts; Described corn straw modification fiber is Modification of Styrene-Acrylate Emulsion corn stalk fiber;
S5, the fluorgypsum obtaining is put into curing field maintenance 10 days appear on the scene afterwards in S4.
Claims (9)
1. a method of modifying for fluorgypsum, is characterized in that, comprises the following steps:
S1, fluorgypsum is put into grinding in ball grinder pulverize, put into baking oven and heat-treat after sieving, thermal treatment temp is 105-115 ℃, and the time is 5-8h;
S2, alum is put into retort furnace calcine, calcining temperature is 600-650 ℃, and calcination time is 0.8-1.3h, be cooled to after room temperature grind, sieving for standby; Rhombspar is put into retort furnace and calcine, calcining temperature is 700-800 ℃, and calcination time is 1-1.5h, be cooled to after room temperature grind, sieving for standby;
In S3, the fluorgypsum in S1 after thermal treatment, add in calcium hydroxide, blast-furnace slag, S2 the rhombspar after calcining in alum after calcining, S2, stir, standing 10-20h carries out chemical modification one time, and then 250-300 ℃ of calcining, calcination time is 0.5-1.5h; Wherein, add by weight in 1-1.8 part calcium hydroxide, 1-2 part blast-furnace slag, 1-1.5 part S1 the rhombspar after calcining in the alum after calcining, 0.5-0.8 part S2 in the fluorgypsum after every 100 parts of thermal treatments;
In S4, the fluorgypsum in S3 after calcining, add flyash, corn straw modification fiber, wilkinite to carry out secondary chemical modification; Wherein, in the fluorgypsum after every 100 parts of calcinings, add 0.5-0.8 part flyash, 0.5-0.8 part corn straw modification fiber, 1-1.2 part wilkinite by weight; Described corn straw modification fiber is Modification of Styrene-Acrylate Emulsion corn stalk fiber;
S5, the fluorgypsum obtaining is put into curing field maintenance 10 days appear on the scene afterwards in S4.
2. the method for modifying of fluorgypsum according to claim 1, is characterized in that, in S1, thermal treatment temp is 110-113 ℃, and the time is 6-7h.
3. the method for modifying of fluorgypsum according to claim 2, is characterized in that, in S1, thermal treatment temp is 112 ℃, and the time is 6.3h.
4. according to the method for modifying of the fluorgypsum described in any one in claim 1-3, it is characterized in that, in S3, the fluorgypsum in S1 after thermal treatment carries out after a chemical modification, and 285-295 ℃ of calcining, calcination time is 0.8-1.2h.
5. the method for modifying of fluorgypsum according to claim 4, is characterized in that, in S3, the fluorgypsum in S1 after thermal treatment carries out after a chemical modification, and 290 ℃ of calcinings, calcination time is 1.0h.
6. according to the method for modifying of the fluorgypsum described in any one in claim 1-5, it is characterized in that, in S3, in a chemical modification, in the fluorgypsum after every 100 parts of thermal treatments, add by weight in 1.2-1.6 part calcium hydroxide, 1.5-1.7 part blast-furnace slag, 1.2-1.3 part S2 the rhombspar after calcining in alum after calcining, 0.6-0.65 part S2.
7. the method for modifying of fluorgypsum according to claim 6, it is characterized in that, in S3, in a chemical modification, in the fluorgypsum after every 100 parts of thermal treatments, add by weight in 1.4 parts of calcium hydroxides, 1.6 parts of blast-furnace slags, 1.25 parts of S2 the rhombspar after calcining in the alum after calcining, 0.63 part of S2.
8. according to the method for modifying of the fluorgypsum described in any one in claim 1-7, it is characterized in that, in S4, in secondary chemical modification, in the fluorgypsum after every 100 parts of calcinings, add by weight 0.6-0.68 part flyash, 0.6-0.7 part corn straw modification fiber, 1.1-1.15 part wilkinite.
9. the method for modifying of fluorgypsum according to claim 8, it is characterized in that, in S4, in secondary chemical modification, in the fluorgypsum after every 100 parts of calcinings, add by weight 0.65 part of flyash, 0.68 part of corn straw modification fiber, 1.13 parts of wilkinites.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107915464A (en) * | 2017-11-30 | 2018-04-17 | 明光市裕阳新材料有限公司 | A kind of antibacterial light cellular partition board and preparation method thereof |
| CN115073112A (en) * | 2022-06-10 | 2022-09-20 | 四川方大新型建材科技开发有限责任公司 | Gypsum-based self-leveling mortar and preparation method thereof |
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| CN107915464A (en) * | 2017-11-30 | 2018-04-17 | 明光市裕阳新材料有限公司 | A kind of antibacterial light cellular partition board and preparation method thereof |
| CN115073112A (en) * | 2022-06-10 | 2022-09-20 | 四川方大新型建材科技开发有限责任公司 | Gypsum-based self-leveling mortar and preparation method thereof |
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