CN103553385A - Method for preparing high-strength alpha-semi-hydrated gypsum from flue gas desulfurization gypsum - Google Patents
Method for preparing high-strength alpha-semi-hydrated gypsum from flue gas desulfurization gypsum Download PDFInfo
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Abstract
The invention belongs to the field of material science, and relates to a method for preparing high-strength alpha-semi-hydrated gypsum from flue gas desulfurization gypsum. The method comprises the following steps: 1) preparing desulfurization gypsum slurry: sufficiently mixing the flue gas desulfurization gypsum and water according to a solid-liquid mass ratio of 1: (4-10), and warming to 80-95 DEG.C; 2) adding a habit modifier to prepare mixed slurry: adding the habit modifier in the desulfurization gypsum slurry according to a condition that the mass ratio of the flue gas desulfurization gypsum to the habit modifier is 1: (0.5-1.5), wherein the habit modifier is a mixture of magnesium chloride hexahydrate and magnesium sulfate hexahydrate in a mass ratio of 1: (0.1-0.2), continuously warming to boil, and refluxing; 3) adding a crystal habit modifier: adding the crystal habit modifier in the mixed slurry obtained in the step 2) according to a condition that the mass ratio of the flue gas desulfurization gypsum to the crystal habit modifier is 1: (1%-5%); and 4) crystal transforming. The uniform short hexagonal prism alpha-semi-hydrated gypsum can be prepared by the method simple in process, the rupture strength reaches 14.4 MPa, and the compressive strength reaches 44.5 MPa.
Description
Technical field
The invention belongs to material science.Relate to a kind of preparation method of desulfurized gesso of flue gas as main material production high strength α-type semi-hydrated gypsum of take.
Background technology
In recent years, due to the requirement of environment protection, national Ge great heat power plant had installed flue gas desulfurization (FGD) unit in succession.This just brings another environmental issue: in flue gas desulfurization course, produced a large amount of by product-desulfurized gesso of flue gas, yet FGD gypsum becomes solid waste., desulfurized gesso of flue gas reaches more than 95% containing terra alba, and its grade and the plaster of paris are suitable.It can the dehydrated semi-hydrated gypsum that becomes.Semi-hydrated gypsum is divided into alpha-semi water plaster stone and β-semi-hydrated gypsum.Alpha-semi water plaster stone is more complete than β-semi-hydrated gypsum compact crystallization, and coarse grains is even, and water paste ratio is low.Thereby having higher intensity, purposes is more extensive.
By desulfurized gesso of flue gas Dehydration, for alpha-semi water plaster stone, mainly contain autoclave method, hydrothermal method and normal pressure salt solustion mehtod.Wherein autoclave method and hydrothermal method need larger facility investment, and normal pressure salt solustion mehtod is that desulfurated plaster segmentation is joined in certain density salts solution, adds some auxiliary agents, mixture is heated to boiling temperature Dehydration under normal pressure for alpha-semi water plaster stone.The maximum feature of the method is that equipment is simple, operation is easy to control, be convenient to industrialization.But alpha-semi water plaster stone crystallization belongs to thermodynamic unstable system in salts solution, in different solution environmentals, with needle-like, column, the crystal habit such as granular, occur.Needle-like alpha-semi water plaster stone has higher water paste ratio, and intensity is less; And granular and column alpha-semi water plaster stone has lower water paste ratio, intensity is larger.In patent CN101113084A; contriver discloses normal pressure salt solustion mehtod and has prepared the controlled alpha-semi water plaster stone of pattern; the steps include: that (1) is 1:(4～10 in desulfurized gesso of flue gas and water solid-liquid mass ratio) ratio make water-soluble serous; add medium crystallization agent (for water-soluble serous quality 5%～21%); stir; be heated to 80～95 ℃, with mineral acid, slurries pH be adjusted to 1.0～5.5; (2) add crystal habit modifying agent and stablizer.Utilize this method, the alpha-semi water plaster stone folding strength of the granular crystal that can make reaches 7.7MPa, and ultimate compression strength reaches 33MPa.
Summary of the invention
In order further to improve the intensity of prepared alpha-semi water plaster stone, the invention provides and a kind ofly take desulfurized gesso of flue gas as main raw material, under atmospheric pressure adopt salts solution Dehydration for the method for alpha-semi water plaster stone.The method process is simple, can make uniform short hexagonal columnar alpha-semi water plaster stone, and folding strength reaches 14.4MPa, and ultimate compression strength reaches 44.5MPa.
The preparation of the alpha-semi water plaster stone of the short hexagonal columnar of high strength provided by the invention, its technical scheme mainly comprises the following steps:
1) preparation of desulfurated plaster slurries: desulfurized gesso of flue gas is fully mixed and is then warming up to 80～95 ℃ by solid-liquid mass ratio 1:4～10 with water.
2) add medium crystallization agent to make mixed slurry: by desulfurized gesso of flue gas and medium crystallization agent mass ratio 1:0.5～1.5, to add in desulfurated plaster slurries, medium crystallization agent is the mixture of magnesium chloride hexahydrate and six water magnesium sulfates, and the mass ratio of magnesium chloride hexahydrate and six water magnesium sulfates is 1:0.1～0.2; Continue to be warming up to boiling, reflux.
3) add crystal habit modifying agent: by desulfurized gesso of flue gas and crystal habit modifying agent mass ratio 1:1%～5%, add through step 2) in the mixed serum that obtains.
4) turn brilliant: the mixed slurry that has added crystal habit modifying agent is refluxed under boiling temperature, complete terra alba to the crystal conversion of alpha-semi water plaster stone.
5) filter and wash.
As preferred implementation, in step 1), desulfurized gesso of flue gas is fully mixed by solid-liquid mass ratio 1:4.84 with water; Step 2), in, desulfurized gesso of flue gas is fully mixed by solid-liquid mass ratio 1:0.93 with water; In step 3), the crystal habit modifying agent adding is succinic acid, by desulfurized gesso of flue gas and crystal habit modifying agent mass ratio 1:4.83%, adds.
The invention has the advantages that preparation process is simple, by the effect of medium crystallization agent and crystal habit modifying agent, desulfurated plaster dewaters in salts solution, the length-to-diameter ratio that has obtained homogeneous is less than 1 short hexagonal columnar alpha-semi water plaster stone, folding strength reaches 14.4MPa, it is that equipment is simple, convenient operation is controlled, is easy to industrialization, with short production cycle that ultimate compression strength reaches 44.5MPa. another feature of the present invention, and salts solution can recycle.Therefore, enforcement of the present invention can reduce the exploitation in plaster of paris ore deposit, can turn waste into wealth again, and protection of the environment.
Accompanying drawing explanation
The SEM photo of Fig. 1 alpha-semi water plaster stone crystal morphology, the length-to-diameter ratio of crystal is less than 1(and adds crystal habit modifying agent).
Fig. 2. the SEM photo of alpha-semi water plaster stone crystal morphology, the length-to-diameter ratio of crystal is greater than 1(and does not add crystal habit modifying agent).
Specific embodiments
The preparation of the alpha-semi water plaster stone of the short hexagonal columnar of high strength provided by the invention, its technical scheme mainly comprises the following steps:
1) preparation of desulfurated plaster slurries: desulfurized gesso of flue gas is mixed by solid-liquid mass ratio 1:4～10 with water, stir and fully mix for 1～2 hour, be then warming up to 80～95 ℃.
2) add medium crystallization agent to make mixed slurry: by desulfurized gesso of flue gas and medium crystallization agent mass ratio 1:0.5～1.5, to add in the desulfurated plaster slurries that obtain through step 1), medium crystallization agent is the mixture of magnesium chloride hexahydrate and six water magnesium sulfates, and the mass ratio of magnesium chloride hexahydrate and six water magnesium sulfates is 1:0.1～0.2; Continue to be warming up to boiling (107～108 ℃), reflux.
3) adding crystal habit modifying agent: by desulfurized gesso of flue gas and crystal habit modifying agent mass ratio 1:1%～5%, add through step 2) in the mixed serum that obtains, the crystal habit modifying agent adding is succinic acid.Mixed serum bumping, makes saturated solution by succinic acid in advance when adding succinic acid.
4) turn brilliant: the interpolation that step 3) is obtained the mixed slurry of crystal habit modifying agent at boiling temperature (107～108 ℃), reflux 1～2 hour, complete terra alba to the crystal conversion of alpha-semi water plaster stone.
5) filter and wash: the alpha-semi water plaster stone mixed slurry filtered while hot that step 4) is obtained, filter cake is dried 2～4 hours at 80 ℃.Filtrate cycle is used.
Below in conjunction with a typical embodiment, the present invention will be described.62 kilograms of desulfurized gesso of flue gas are put into reactor with 300 liters of tap water, stir 1 hour fully homogeneous slurries of mixed formation, be then warming up to 85 ℃.In reactor, add 52 kilograms of magnesium chloride hexahydrates and 6 kilogram of six water magnesium sulfate.Stirring and dissolving continues to be warming up to boiling (107～108 ℃).3 kilograms of succinic acid are dissolved in 2 premium on currency, slowly join in reactor, start to turn brilliant, maintain the temperature at 107～108 ℃, stirring velocity is 60 revs/min.Reflux after 1.5 hours, microscopic examination shows that desulfurized gesso of flue gas is transformed into the alpha-semi water plaster stone of short hexagonal columnar completely. filtered while hot, filtrate use to be recycled.Filter cake washs with approximately 500 liters of 80 ℃ of hot tap waters.Filter cake after washing is put into 80 ℃ of loft drier and is dried 3 hours, obtains high strength alpha-semi water plaster stone, makes to obtain standard model folding strength 14.4MPa, and ultimate compression strength 44.5MPa. hot wash-water can be recycled.Referring to Fig. 1 and Fig. 2, to add after crystal habit modifying agent, the length-to-diameter ratio of crystal is less than 1, grain size homogeneous.
Claims (3)
1. with desulfurized gesso of flue gas, prepare a method for high strength alpha-semi water plaster stone, comprise the following steps:
1) preparation of desulfurated plaster slurries: desulfurized gesso of flue gas is fully mixed and is then warming up to 80～95 ℃ by solid-liquid mass ratio 1:4～10 with water.
2) add medium crystallization agent to make mixed slurry: by desulfurized gesso of flue gas and medium crystallization agent mass ratio 1:0.5～1.5, to add in desulfurated plaster slurries, medium crystallization agent is the mixture of magnesium chloride hexahydrate and six water magnesium sulfates, and the mass ratio of magnesium chloride hexahydrate and six water magnesium sulfates is 1:0.1～0.2; Continue to be warming up to boiling, reflux;
3) add crystal habit modifying agent: by desulfurized gesso of flue gas and crystal habit modifying agent mass ratio 1:1%～5%, add through step 2) in the mixed serum that obtains;
4) turn brilliant: the mixed slurry that has added crystal habit modifying agent is refluxed under boiling temperature, complete terra alba to the crystal conversion of alpha-semi water plaster stone;
5) filter and wash.
2. the method for preparing high strength alpha-semi water plaster stone with desulfurized gesso of flue gas according to claim 1, is characterized in that, in step 1), desulfurized gesso of flue gas is fully mixed by solid-liquid mass ratio 1:4.84 with water.
2. the method for preparing high strength alpha-semi water plaster stone with desulfurized gesso of flue gas according to claim 1, is characterized in that step 2) in, desulfurized gesso of flue gas is fully mixed by solid-liquid mass ratio 1:0.93 with water.
3. the method for preparing high strength alpha-semi water plaster stone with desulfurized gesso of flue gas according to claim 1, it is characterized in that, in step 3), the crystal habit modifying agent adding is succinic acid, by desulfurized gesso of flue gas and crystal habit modifying agent mass ratio 1:4.83%, adds.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045305A (en) * | 2014-06-27 | 2014-09-17 | 天津大学 | Method for enhancing strength of alpha-type semi-hydrated gypsum hydrated and hardened body by using white latex as modifier |
| CN104499041A (en) * | 2015-01-15 | 2015-04-08 | 河南城建学院 | Cyclic utilization method for using desulfurization gypsum to prepare calcium sulfate crystal whisker filtrate |
| CN105174760A (en) * | 2015-09-18 | 2015-12-23 | 金正大生态工程集团股份有限公司 | Method for preparing alpha semi-hydrated gypsum from dihydrate gypsum |
| CN108863126A (en) * | 2018-08-29 | 2018-11-23 | 宁波金泽新型建材有限公司 | A method of alpha-semi water plaster stone is prepared using desulfurized gesso of flue gas |
| CN112299468A (en) * | 2020-10-30 | 2021-02-02 | 山东聚鑫新材料有限公司 | Flaky calcium sulfate crystal and preparation method thereof |
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| US5248487A (en) * | 1987-03-21 | 1993-09-28 | Jorg Bold | Process for the conversion of calcium sulfate dihydrate into alpha-hemihydrate |
| CN101113084A (en) * | 2007-07-06 | 2008-01-30 | 天津大学 | Method for preparing shape-controlled alpha-semi-hydrated gypsum by using flue gas desulfurized gypsum |
| CN101302029A (en) * | 2008-06-26 | 2008-11-12 | 武汉科技大学 | Method for preparing alpha-hemihydrate gypsum with desulfurated gypsum |
| CN101734871A (en) * | 2008-11-18 | 2010-06-16 | 北京建筑材料科学研究总院有限公司 | Method for preparing alpha semi-hydrated gypsum by utilizing desulfurized gypsum |
| EP2418184A2 (en) * | 2010-08-12 | 2012-02-15 | Lindner GFT GmbH | Method for manufacturing alpha-calcium sulphate hemi-hydrate |
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Patent Citations (5)
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| US5248487A (en) * | 1987-03-21 | 1993-09-28 | Jorg Bold | Process for the conversion of calcium sulfate dihydrate into alpha-hemihydrate |
| CN101113084A (en) * | 2007-07-06 | 2008-01-30 | 天津大学 | Method for preparing shape-controlled alpha-semi-hydrated gypsum by using flue gas desulfurized gypsum |
| CN101302029A (en) * | 2008-06-26 | 2008-11-12 | 武汉科技大学 | Method for preparing alpha-hemihydrate gypsum with desulfurated gypsum |
| CN101734871A (en) * | 2008-11-18 | 2010-06-16 | 北京建筑材料科学研究总院有限公司 | Method for preparing alpha semi-hydrated gypsum by utilizing desulfurized gypsum |
| EP2418184A2 (en) * | 2010-08-12 | 2012-02-15 | Lindner GFT GmbH | Method for manufacturing alpha-calcium sulphate hemi-hydrate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045305A (en) * | 2014-06-27 | 2014-09-17 | 天津大学 | Method for enhancing strength of alpha-type semi-hydrated gypsum hydrated and hardened body by using white latex as modifier |
| CN104045305B (en) * | 2014-06-27 | 2016-08-24 | 天津大学 | Milky white adhesive is the method that modifying agent strengthens alpha semi-hydrated gypsum hydration and hardening body intensity |
| CN104499041A (en) * | 2015-01-15 | 2015-04-08 | 河南城建学院 | Cyclic utilization method for using desulfurization gypsum to prepare calcium sulfate crystal whisker filtrate |
| CN105174760A (en) * | 2015-09-18 | 2015-12-23 | 金正大生态工程集团股份有限公司 | Method for preparing alpha semi-hydrated gypsum from dihydrate gypsum |
| CN108863126A (en) * | 2018-08-29 | 2018-11-23 | 宁波金泽新型建材有限公司 | A method of alpha-semi water plaster stone is prepared using desulfurized gesso of flue gas |
| CN108863126B (en) * | 2018-08-29 | 2021-03-30 | 宁波金泽新型建材有限公司 | Method for preparing alpha-semi-hydrated gypsum by using flue gas desulfurization gypsum |
| CN112299468A (en) * | 2020-10-30 | 2021-02-02 | 山东聚鑫新材料有限公司 | Flaky calcium sulfate crystal and preparation method thereof |
| CN112299468B (en) * | 2020-10-30 | 2022-12-30 | 山东聚鑫新材料有限公司 | Flaky calcium sulfate crystal and preparation method thereof |
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Application publication date: 20140205 |