CN103964714A - Method for preparing high-performance gypsum-based composite cementing material by calcium sulfite type FGD (Flue Gas Desulfurization) gypsum - Google Patents
Method for preparing high-performance gypsum-based composite cementing material by calcium sulfite type FGD (Flue Gas Desulfurization) gypsum Download PDFInfo
- Publication number
- CN103964714A CN103964714A CN201410178619.1A CN201410178619A CN103964714A CN 103964714 A CN103964714 A CN 103964714A CN 201410178619 A CN201410178619 A CN 201410178619A CN 103964714 A CN103964714 A CN 103964714A
- Authority
- CN
- China
- Prior art keywords
- gypsum
- calcium sulfite
- sulfite type
- based composite
- cementing material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a method for preparing a gypsum-based composite cementing material. The method comprises the following steps: (1) mixing the calcium sulfite type FGD (Flue Gas Desulfurization) gypsum with modifiers thoroughly, wherein the mineral modifier is 10-30% of fly ash (or coal gangue), and the chemical modifier is 1-5% of a soluble sulfate; (2) placing the thoroughly-mixed calcium sulfite type FGD gypsum and the modifiers in a fluidized bed furnace with the temperature of 450-650 DEG C (or using waste gas from power plants as well as iron and steel enterprises for heating); keeping calcining for 20-40 min under oxidizing atmosphere, wherein the calcium sulfite is oxidized into type II anhydrite and the fly ash (or the coal gangue) absorbs residual alkali desulfurizer to be activated into active fly ash ( or active coal gangue). The gypsum-based composite cementing material prepared through the method has the advantages of high strength, high water resistance, low carbon, environmental friendliness and the like. The method adopts a simple process, can utilize waste gas resource generated by power plants or steel mills during heating, is an effective method for solving the difficulty that calcium sulfite type FGD gypsum cannot be utilized efficiently, reduces pollution, and is beneficial to popularization of dry and semi-dry FGD processes.
Description
Technical field
The invention belongs to waste residue modification treatment and comprehensive utilization field, especially the present invention relates to a kind of method of utilizing calcium sulfite type desulphurization gypsum to prepare high-performance gypsum based composite cementing material.
Background technology
Because China's topsoil is day by day serious, national awareness of environment protection constantly strengthens in recent years, and country is more and more stricter to the flue gas desulfurization processing requirements of the enterprise such as power plant, steel mill, has also produced a large amount of desulfurizing byproducts simultaneously.By 2013, China discharged nearly hundred million tons of desulfurizing byproducts every year, and wherein calcium sulfite type desulphurization gypsum accounts for more than 1,000 ten thousand t, and quantity discharged is all increasing every year.Main flow sulfur removal technology can divide three kinds now: dry desulfurization, semi-dry desulphurization and wet desulphurization.According to the difference of sulfur removal technology, desulfurizing byproduct is broadly divided into two classes: dry method/semidrying calcium sulfite type desulphurization gypsum, wet desulphurization gypsum.At present, the application of wet desulphurization gypsum is very ripe, but the comprehensive utilizating research for calcium sulfite type desulphurization gypsum is less, a large amount of calcium sulfite type desulphurization gypsum is still stacked in the open, not only environment is caused to secondary pollution, also can land occupation resource, rationally not applied be also a kind of waste of resource to calcium sulfite type desulphurization gypsum in addition.
The physicochemical property of calcium sulfite type desulphurization gypsum produces very large disadvantageous effect to its comprehensive utilization.In calcium sulfite type desulphurization gypsum, there is unreacted sweetening agent (being generally calcium oxide or calcium hydroxide) and a large amount of calcium sulfites, if directly widely apply in gelling material is produced, too high calcium hydroxide and calcium sulfite can make product volume expand in hydration process, cause the volume stability of goods bad, in view of above reason, the recycling of calcium sulfite type desulphurization gypsum is restricted, and not yet forms industrialization.At present calcium sulfite type desulphurization gypsum being carried out to low-temperature oxidation processing, is calcium sulfate (II type dehydrated gyp-) calcium sulfite oxidation wherein, prepares gypsum based gel material, be a kind of added value higher utilize method.It is II type dehydrated gyp-by calcined oxide calcium sulfite type desulphurization gypsum that patent CN102701618A proposes, mix again the auxiliary materials such as exciting agent, water-holding agent, adjustable solidification agent, successfully prepare the high-strength environment-friendly whitewash gypsum that meets JC/T517-2004 " brushing gypsum " standard.The method does not make full use of residual alkaline sweetening agent in calcium sulfite type desulphurization gypsum, and residual alkaline sweetening agent exists harmful effect to the performance of gypsum.Present method proposes to mix appropriate flyash (coal gangue) component in the time of low temperature calcination oxidation calcium sulfite type desulphurization gypsum, flyash when calcining (coal gangue) and residual alkaline reactive desulfurizing agent, obtain active fly ash (coal gangue), intensity and water tolerance to gypsum based composite cementing material improve significantly.
Summary of the invention
The object of the present invention is to provide a kind of method of effectively utilizing calcium sulfite type desulphurization gypsum, a kind of method of utilizing calcium sulfite type desulphurization gypsum to prepare high-performance gypsum based composite cementing material is provided.
For achieving the above object, the present invention has taked following technical scheme:
Utilize calcium sulfite type desulphurization gypsum to prepare a method for high-performance gypsum based composite cementing material, comprise the following steps:
(1) in calcium sulfite type desulphurization gypsum, add modification agent with chemical modifier and mixed, wherein modification agent is 10-30% flyash (coal gangue); Chemical modifier is 1-5% soluble sulphate;
(2) the calcium sulfite type desulphurization gypsum mixing and properties-correcting agent are placed in to fluidizing furnace (or utilizing the waste gas of generating and iron and steel enterprise as thermal source), continue to blast air at described fluidizing furnace blast orifice, making fluidizing furnace inner is oxidizing atmosphere, and make described calcium sulfite type desulphurization gypsum and properties-correcting agent in boiling state, be to calcine under the condition of 450-650 DEG C in temperature, after 20-40min, change its main component calcium sulfite and flyash (coal gangue) into II type dehydrated gyp-and activating fly ash (coal gangue).
Preferably, the mode of mixing in described step (1) be modification agent for being uniformly mixed, chemical modifier is first fully soluble in water, mixes being uniformly mixed in process with spray pattern.
Preferably, calcinating system is that 450-650 DEG C, oxidizing atmosphere, time are 20-40min in described step (2).。
The present invention, by calcium sulfite type desulphurization gypsum and properties-correcting agent are carried out to mixed calcining processing, obtains calcining calcium sulfite type desulphurization gypsum (calcium sulfite content is lower than 5%), can be applied to production gypsum based composite cementing material.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention calcines calcium sulfite type desulphurization gypsum and properties-correcting agent for II type dehydrated gyp-and activating fly ash (coal gangue) under oxidizing atmosphere condition, thereby is prepared into gypsum based composite cementing material.
2, in the present invention by flyash (coal gangue) and CaO or Ca (OH)
2the calcium sulfite type desulphurization gypsum that content is higher mixes rear calcining, can activating fly ash (coal gangue), make its (3-7 days) just energy hydration reaction generation intensity and higher CSH gel, ettringite etc. of water tolerance in early days, thereby improved intensity and the water tolerance of gypsum based composite cementing material.
3, the present invention has good economic benefit, social benefit and environmental benefit.This research meets the fundamental policy that national energy-saving reduces discharging, and has both protected ecotope, has brought new growth engines again for coal-fired enterprise, has really realized and having turned waste into wealth, and turns bane into boon, and plays to alleviating the environmental stress that brings of industrial production the effect of demonstrating of taking the lead
Embodiment
Embodiment 1:
The raw material that utilizes calcium sulfite type desulphurization gypsum to prepare gypsum based composite cementing material in the present embodiment is constructed as follows by mass fraction:
Calcium sulfite type desulphurization gypsum 90%, flyash 10%, mixes 3% alum and 1% anhydrous sodium sulphate outward.
Calcium sulfite type desulphurization gypsum and flyash are uniformly mixed, and chemical modifier is first fully soluble in water, mix being uniformly mixed in process in the mode of spraying.
The calcium sulfite type desulphurization gypsum mixing is placed in to fluidizing furnace, continue to blast air at described fluidizing furnace blast orifice, making fluidizing furnace inner is oxidizing atmosphere, and make described calcium sulfite type desulphurization gypsum and properties-correcting agent in boiling state, be to calcine under the condition of 450 DEG C in temperature, insulation 30min.The gypsum based composite cementing material performance test of preparing in the present embodiment is in table 1.
Table 1 gypsum based composite cementing material salient features
| Project | Performance index |
| Standard consistency (%) | 40 |
| Time of coagulation (min) | Initial set 109, final set 145 |
| Contract with dry rate (mm/m) | 0.42 |
| Ultimate compression strength (MPa) | 2.65(3d)、3.23(7d)、4.84(28d) |
| Folding strength (MPa) | 0.58(3d)、0.78(7d)、1.02(28d) |
| Coefficient of softening | 0.61 |
Embodiment 2:
The raw material that utilizes calcium sulfite type desulphurization gypsum to prepare gypsum based composite cementing material in the present embodiment is constructed as follows by mass fraction:
Calcium sulfite type desulphurization gypsum 80%, flyash 20%, mixes 3% alum and 1% anhydrous sodium sulphate outward.
Calcium sulfite type desulphurization gypsum and flyash are uniformly mixed, and chemical modifier is first fully soluble in water, mix being uniformly mixed in process in the mode of spraying.
The calcium sulfite type desulphurization gypsum mixing is placed in to fluidizing furnace, continue to blast air at described fluidizing furnace blast orifice, making fluidizing furnace inner is oxidizing atmosphere, and make described calcium sulfite type desulphurization gypsum and properties-correcting agent in boiling state, be to calcine under the condition of 550 DEG C in temperature, insulation 30min.The gypsum based composite cementing material performance test of preparing in the present embodiment is in table 2
Table 2 gypsum based composite cementing material salient features
| Project | Performance index |
| Standard consistency (%) | 41 |
| Time of coagulation (min) | Initial set 130, final set 175 |
| Contract with dry rate (mm/m) | 0.36 |
| Ultimate compression strength (MPa) | 7.68(3d)、8.63(7d)、10.85(28d) |
| Folding strength (MPa) | 1.71(3d)、2.46(7d)、3.29(28d) |
| Coefficient of softening | 0.71 |
Embodiment 3:
The raw material that utilizes calcium sulfite type desulphurization gypsum to prepare gypsum based composite cementing material in the present embodiment is constructed as follows by mass fraction:
Calcium sulfite type desulphurization gypsum 70%, flyash 30%, mixes 3% alum and 1% anhydrous sodium sulphate outward.
Calcium sulfite type desulphurization gypsum and flyash are uniformly mixed, and chemical modifier is first fully soluble in water, mix being uniformly mixed in process in the mode of spraying.
The calcium sulfite type desulphurization gypsum mixing is placed in to fluidizing furnace, continue to blast air at described fluidizing furnace blast orifice, making fluidizing furnace inner is oxidizing atmosphere, and make described calcium sulfite type desulphurization gypsum and properties-correcting agent in boiling state, be to calcine under the condition of 650 DEG C in temperature, insulation 30min.The gypsum based composite cementing material performance test of preparing in the present embodiment is in table 3
Table 3 gypsum based composite cementing material salient features
| Project | Performance index |
| Standard consistency (%) | 34 |
| Time of coagulation (min) | Initial set 150, final set 227 |
| Contract with dry rate (mm/m) | 0.31 |
| Ultimate compression strength (MPa) | 10.46(3d)、15.77(7d)、16.98(28d) |
| Folding strength (MPa) | 2.61(3d)、3.38(7d)、4.26(28d) |
| Coefficient of softening | 0.83 |
Claims (5)
1. utilize calcium sulfite type desulphurization gypsum to prepare a method for high-performance gypsum based composite cementing material, it is characterized in that comprising the following steps:
(1) in calcium sulfite type desulphurization gypsum, add modification agent and chemical modifier, and mix, wherein modification agent is 10-30% flyash (coal gangue), and chemical modifier is for mixing 1-5% soluble sulphate outward;
(2) the calcium sulfite type desulphurization gypsum mixing and properties-correcting agent are placed in to fluidizing furnace (or utilizing generating and iron and steel enterprise's waste gas) heating.Continue to blast air at described fluidizing furnace blast orifice, making fluidizing furnace inner is oxidizing atmosphere, and make described calcium sulfite type desulphurization gypsum and properties-correcting agent in boiling state, be to calcine under the condition of 450-650 DEG C in temperature, after 20-40min, change its main component calcium sulfite and flyash (coal gangue) into II type dehydrated gyp-and activating fly ash (coal gangue).
2. the method for utilizing calcium sulfite type desulphurization gypsum to prepare gypsum based composite cementing material according to claim 1, it is characterized in that, in described step (1), the modification agent of calcium sulfite type desulfurated plaster is 10-30% flyash (coal gangue), and chemical modifier is 1-5% soluble sulphate.
3. the method for utilizing calcium sulfite type desulphurization gypsum to prepare gypsum based composite cementing material according to claim 1, it is characterized in that the hybrid mode of calcium sulfite type desulfurated plaster and properties-correcting agent in described step (1): modification agent is for being uniformly mixed; Chemical modifier is first fully soluble in water, mixes being uniformly mixed in process with spray pattern.
4. the method for utilizing calcium sulfite type desulphurization gypsum to prepare gypsum based composite cementing material according to claim 1, is characterized in that, the water ratio of the calcium sulfite type desulphurization gypsum mixing in described step (1) is 10-15%.
5. the method for utilizing calcium sulfite type desulphurization gypsum to prepare gypsum based composite cementing material according to claim 1, is characterized in that, in described step (2), calcinating system is 450-650 DEG C, atmospheric oxidation atmosphere, and the time is 20-40min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410178619.1A CN103964714B (en) | 2014-04-25 | 2014-04-25 | A kind of method utilizing calcium sulfite type desulphurization gypsum to prepare high-performance gypsum based composite cementing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410178619.1A CN103964714B (en) | 2014-04-25 | 2014-04-25 | A kind of method utilizing calcium sulfite type desulphurization gypsum to prepare high-performance gypsum based composite cementing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103964714A true CN103964714A (en) | 2014-08-06 |
| CN103964714B CN103964714B (en) | 2016-04-13 |
Family
ID=51234780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410178619.1A Expired - Fee Related CN103964714B (en) | 2014-04-25 | 2014-04-25 | A kind of method utilizing calcium sulfite type desulphurization gypsum to prepare high-performance gypsum based composite cementing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103964714B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529207A (en) * | 2014-12-04 | 2015-04-22 | 肇庆北新建材有限公司 | Method for preparing gypsum clinker by utilization of fly ash in circulating fluidized bed boiler |
| CN110981242A (en) * | 2019-12-11 | 2020-04-10 | 西南科技大学 | Method for preparing high-strength anhydrous gypsum from calcium sulfide slag |
| WO2024058749A1 (en) * | 2022-09-14 | 2024-03-21 | Dalsan Yatirim Ve Enerji Anonim Sirketi | A plaster firing oven with zero carbon emission |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0230793A2 (en) * | 1986-01-07 | 1987-08-05 | BPB INDUSTRIES public limited company | Calcination method and apparatus for gypsum or similar materials |
| CN1631830A (en) * | 2004-12-22 | 2005-06-29 | 中国建筑材料科学研究院 | Gangue active mixed material, its preparation method and high-performance cement |
| CN102515595A (en) * | 2011-11-22 | 2012-06-27 | 上海市建筑科学研究院(集团)有限公司 | Composite cementitious material of desulfurated waste residue and mortar prepared from same |
| CN102701618A (en) * | 2012-06-25 | 2012-10-03 | 甘肃省建材科研设计院 | Method for using calcium sulfite type desulfurization gypsum to produce high-strength environmental-friendly type plastering gypsum |
-
2014
- 2014-04-25 CN CN201410178619.1A patent/CN103964714B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0230793A2 (en) * | 1986-01-07 | 1987-08-05 | BPB INDUSTRIES public limited company | Calcination method and apparatus for gypsum or similar materials |
| CN1631830A (en) * | 2004-12-22 | 2005-06-29 | 中国建筑材料科学研究院 | Gangue active mixed material, its preparation method and high-performance cement |
| CN102515595A (en) * | 2011-11-22 | 2012-06-27 | 上海市建筑科学研究院(集团)有限公司 | Composite cementitious material of desulfurated waste residue and mortar prepared from same |
| CN102701618A (en) * | 2012-06-25 | 2012-10-03 | 甘肃省建材科研设计院 | Method for using calcium sulfite type desulfurization gypsum to produce high-strength environmental-friendly type plastering gypsum |
Non-Patent Citations (2)
| Title |
|---|
| 宋旭艳等: "煤矸石活化过程中结构特性和力学性能的研究", 《硅酸盐学报》 * |
| 方荣利等: "提高粉煤灰活性方法研究", 《水泥》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529207A (en) * | 2014-12-04 | 2015-04-22 | 肇庆北新建材有限公司 | Method for preparing gypsum clinker by utilization of fly ash in circulating fluidized bed boiler |
| CN110981242A (en) * | 2019-12-11 | 2020-04-10 | 西南科技大学 | Method for preparing high-strength anhydrous gypsum from calcium sulfide slag |
| CN110981242B (en) * | 2019-12-11 | 2022-02-11 | 西南科技大学 | Method for preparing high-strength anhydrous gypsum from calcium sulfide slag |
| WO2024058749A1 (en) * | 2022-09-14 | 2024-03-21 | Dalsan Yatirim Ve Enerji Anonim Sirketi | A plaster firing oven with zero carbon emission |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103964714B (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103241966B (en) | Clinker free regenerated slag micro-powder compound cement | |
| CN104478255B (en) | A kind of magnesium oxysulfide concrete containing magnesia FGD waste liquid and preparation method thereof | |
| CN103771734B (en) | A kind of mass-producing calcination processing utilizes the method for electrolytic manganese residues | |
| CN104556882B (en) | A kind of method of the concrete product utilizing construction material manufacture to have carbon sequestration function | |
| CN102079635B (en) | Desulfurization gypsum clinker-free steel slag cement | |
| CN101386494A (en) | Composite gelate material and preparation method thereof | |
| CN102838153B (en) | Method for producing vitriol and calcium oxide by decomposing gypsum | |
| CN102515588A (en) | Ecotypic cementing material | |
| CN104556909B (en) | A kind of be raw material with flyash fast solidifying anti-corrosion cement and preparation method thereof | |
| CN107445498B (en) | Preparation method of phosphogypsum-fly ash composite cementing material | |
| CN103964714B (en) | A kind of method utilizing calcium sulfite type desulphurization gypsum to prepare high-performance gypsum based composite cementing material | |
| CN105621909B (en) | It is a kind of to mix modified Desulphurization and the cement of rice hull ash again | |
| CN113880540A (en) | Method for preparing gypsum self-leveling material by using semi-dry method to oxidize desulfurized ash | |
| CN110183202A (en) | A kind of unburned ecological brick and preparation method thereof of subway engineering discarded slurry preparation | |
| CN105384375A (en) | Active admixture for building materials | |
| CN104513037A (en) | Cement prepared with sintered dry desulfurization ash as cement retarder and preparation method of the cement | |
| CN105541150A (en) | An active admixture prepared by utilizing semi-dry process desulfurized fly ash | |
| CN108585575B (en) | Cement retarder and preparation method and application thereof | |
| CN102206056B (en) | Preparation method of concrete waterproofer with industrial by-product gysum non-calcining technology | |
| CN103253637A (en) | Method for producing sulfuric acid and calcium oxide by utilizing gypsum | |
| CN107324676B (en) | β-semi-hydrated gypsum method is prepared using low grade coal calcined phosphogypsum and carbide slurry | |
| CN102659329B (en) | Preparation method for quick hardening early strength hydraulic cementing material | |
| CN102225781A (en) | Preparation method of cement delayed coagulant | |
| CN104129939A (en) | Sulphate aluminium cement prepared from modified phosphogypsum and preparation method thereof | |
| CN105819723B (en) | A kind of preparation method of cement expansive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 063009 Hebei province Tangshan City Xinhua West Road No. 46 Applicant after: North China Polytechnics Address before: 063009 Hebei province Tangshan City Xinhua West Road No. 46 Applicant before: Hebei United University |
|
| CB03 | Change of inventor or designer information |
Inventor after: Yang Lirong Inventor after: Liu Zhigang Inventor after: Huo Chao Inventor after: Yao Shaowei Inventor after: Bai Ruiying Inventor after: Wei Qingmin Inventor after: Feng Xiaoxin Inventor before: Liu Zhigang Inventor before: Huo Chao Inventor before: Yao Shaowei Inventor before: Bai Ruiying Inventor before: Yang Lirong Inventor before: Wei Qingmin Inventor before: Feng Xiaoxin |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160413 Termination date: 20200425 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |