CN102173620B - Method for modifying and producing building gypsum powder by utilizing wet fluorgypsum - Google Patents
Method for modifying and producing building gypsum powder by utilizing wet fluorgypsum Download PDFInfo
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- CN102173620B CN102173620B CN 201110026571 CN201110026571A CN102173620B CN 102173620 B CN102173620 B CN 102173620B CN 201110026571 CN201110026571 CN 201110026571 CN 201110026571 A CN201110026571 A CN 201110026571A CN 102173620 B CN102173620 B CN 102173620B
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- fluorgypsum
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- correcting agent
- building gypsum
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- 239000000843 powder Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000010440 gypsum Substances 0.000 title abstract description 21
- 229910052602 gypsum Inorganic materials 0.000 title abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007605 air drying Methods 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000011507 gypsum plaster Substances 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 208000006558 Dental Calculus Diseases 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000011505 plaster Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 238000000643 oven drying Methods 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical group [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Abstract
The invention discloses a method for modifying and producing building gypsum powder by utilizing wet fluorgypsum. The method comprises the following steps: carrying out natural air drying or oven drying on wet fluorgypsum to remove part of free water, preliminarily crushing to below 2mm, and adding part of a modifier composed of a mixture of aluminosilicate, sulfate and calcic compound into the wet fluorgypsum; and roasting at a low temperature of 80-180 DEG C for 1-3 hours, sufficiently mixing the rest of the modifier, and finely grinding to obtain powder of which the particle size is not greater than 0.147mm, thereby obtaining the modified building gypsum powder material which satisfies the requirements in Building Gypsum GB/T9776-2006. In the modified building gypsum powder material, the mass percent of the wet fluorgypsum is 92-98%, and the mass percent of the modifier is 2-8%. The amounts of the modifier added for the two times are respectively 65-85% and 15-35%. The invention has the technical characteristics of short technological process, low roasting temperature, low cost and stable product quality, and the modifier is added by two steps.
Description
Technical field
The invention belongs to the solid waste resource utilization field, relate to the method for producing building gypsum plaster after the wet fluorgypsum modification of a kind of chemical industry byproduct.
Background technology
The waste residue that utilizes conventional wet technique that fluorite and the vitriol oil are at high temperature discharged during the preparing hydrogen fluoric acid adopts the neutralization of milk of lime or carbide slag usually, is sent to the stockyard again and stores up, and the product of storing up like this is referred to as wet fluorgypsum.The long-term wet fluorgypsum of storing up in a large number not only takies a large amount of land resourcess, and needs a large amount of land compensation expense and maintenance cost, has caused heavy burden for enterprise and society.Calcium sulphate content reaches more than 70% in the wet fluorgypsum in stockyard, is a kind of good gypsum resource.The recycling of realizing the wet fluorgypsum in stockyard meets National Sustainable Development Strategies, has important social benefit and economic worth.The wet fluorgypsum generation nature aquation of storing up for a long time is canescence or white, and chief component is selenite (CaSO
42H
2O).Owing to storing up the time limit and differing, wet fluorgypsum extent of hydration is different, and the not complete milk of lime of neutralization of part is arranged in addition, and the fluorine gypsum powder that causes producing exists that basicity is too high, time of coagulation is long, the phenomenons such as the material of construction physical strength of producing is inadequate have had a strong impact on the recycling of wet fluorgypsum.
Summary of the invention
The objective of the invention is the problem that exists in the wet fluorgypsum recycling process, proposed a kind of method of utilizing wet fluorgypsum modification production high quality buildings terra alba.
The objective of the invention is to realize in the following manner:
A kind of method of utilizing wet fluorgypsum modification production building gypsum plaster may further comprise the steps:
1) wet fluorgypsum is removed the free-water of 15-18% through natural air drying or oven dry, and warp is preliminary broken, adds properties-correcting agent and mix in wet fluorgypsum;
The wet fluorgypsum that 2) will add properties-correcting agent carries out low-temperature bake;
3) powder after the roasting is added again properties-correcting agent fully mixes, fine grinding, namely get the modified building plaster powder materials;
The properties-correcting agent total mass per-cent of described wet fluorgypsum mass percent 92-98%, twice adding is 2-8%; The properties-correcting agent consumption of twice adding in front and back is followed successively by 65-85% and the 15-35% of the total consumption of properties-correcting agent.
Described properties-correcting agent is the miscellany of silico-aluminate, vitriol and calcium containing compound.Each composition quality ratio is silico-aluminate in the described properties-correcting agent: vitriol: calcium containing compound=1-5: 0.1-1: 0.1-2.
Described silico-aluminate is one or more in kaolin, aluminum oxide, water glass, the Sodium Silicofluoride, described vitriol is one or more in Tai-Ace S 150, potassium aluminium sulfate, vitriolate of tartar, the zinc sulfate, and described calcium containing compound is one or more in calcium oxide, calcium hydroxide, the calcium chloride.
Step 1) described preliminary degree of crushing is that particle diameter is not more than 2mm.Just broken mode is the modes such as cutting fragmentation or jaw crushing.
Step 2) described maturing temperature is 80-180 ℃, roasting time 1-3h; Preferred maturing temperature is 100-150 ℃, and roasting time is 2h.
Step 2) kiln that adopts during described roasting is rotary kiln, fluidized-bed or fluidizing furnace.Wet fluorgypsum and properties-correcting agent rely on the rotation of roasting kiln or airflow stirring effect to realize fully mixing, stirring in roasting process.
Step 3) described fine grinding is baked powder and properties-correcting agent to be finely ground to particle diameter together be not more than 0.147mm.Described fine grinding mode is the modes such as Vertical Mill, ball milling or the fragmentation of Kun formula.The powder separate mode is that cyclonic separation or fluidizing furnace separate after the fine grinding; Way of recycling is the modes such as cyclonic separation, electricity gather dust after separating.
The present invention is in suitable adding under the properties-correcting agent effect, change the chemical kinetics character of hydration reaction process, improve its dissolution rate and hydration rate, promote the fluorgypsum whisker respectively to even growth, form each to the reticulated structure of whisker prosperity, shorten time of coagulation, improve the crystal early strength, change it into qualified gypsum building material.
In the properties-correcting agent of the present invention, silico-aluminate is mainly used to regulate basicity and the physical strength of fluorine gypsum powder, and vitriol and calcium containing compound are mainly used to regulate the time of coagulation of fluorine gypsum powder, makes it to reach the production application requirement of material of construction powder.
Technological merit of the present invention is exactly that method is simple, and with low cost, technical process is short, and properties-correcting agent adds in two steps, constant product quality.Compared with prior art, can greatly reduce maturing temperature, shorten roasting time (by foreshortening in the 3h about present 8h); Time of coagulation and physical strength and natural gesso are suitable.
The used fluorgypsum properties-correcting agent of the technology of the present invention cost only is 12-20 yuan/ton, and processing cost 30-40 yuan/ton, according to 150-220 yuan/ton of calculating of produce market price, economic benefit is very considerable.
Description of drawings
Fig. 1 is the SEM photo of wet fluorine gypsum powder;
Fig. 2 is the SEM photo of the defective building gypsum plaster of wet fluorgypsum production;
Fig. 3 is the SEM photo of the building gypsum plaster of the inventive method production;
The gypsum material section image that Fig. 4 produces for test the inventive method;
Fig. 5 is process flow diagram of the present invention.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1: the wet fluorgypsum of storing up is through 40 ℃ of prebakes (free-water of removing about 15-18% just breaks requirement to satisfy wet fluorgypsum), take by weighing 94.5% fluorine gypsum powder, properties-correcting agent 5.5% (kaolin+aluminum oxide+water glass 78%, Tai-Ace S 150+zinc sulfate 9%, calcium oxide+calcium chloride 13%) for subsequent use, at first with 94.5% fluorine gypsum powder, 4% properties-correcting agent is after stirrer fully mixes, the control temperature is at 120 ℃ of lower roasting 2h, naturally cooling, add again remaining 1.5% properties-correcting agent, fully stir evenly mixed and be finely ground to below the 0.147mm, namely get modified building fluorine gypsum powder material.Gained modification fluorgypsum material presetting period 4min, final setting time 8.5min, the folding strength 2.56MPa that measures behind the 24h, ultimate compression strength 10.12MPa.Satisfy " plaster of Paris (GB/T9776-2008) " building gypsum plaster requirement fully.
Embodiment 2: the wet fluorgypsum of storing up is through 40 ℃ of prebakes, take by weighing 95% fluorine gypsum powder, properties-correcting agent 5% (kaolin+aluminum oxide+water glass 78%, Tai-Ace S 150+vitriolate of tartar 9%, calcium oxide+calcium chloride 13%) for subsequent use, at first with 95% fluorine gypsum powder, 3% properties-correcting agent is after stirrer fully mixes, the control temperature is at 120 ℃ of lower roasting 2h, naturally cooling, add remaining 2% properties-correcting agent, fully stirring mixes evenly and is finely ground to below the 0.147mm, namely gets modified building fluorine gypsum powder material again.Gained modification fluorgypsum material presetting period 3.5min, final setting time 5min, the folding strength 1.90MPa that measures behind the 24h, ultimate compression strength 3.78MPa.Satisfy " plaster of Paris (GB/T9776-2008) " building gypsum plaster requirement.
Embodiment 3: the wet fluorgypsum of storing up is through 40 ℃ of prebakes, take by weighing 97% fluorine gypsum powder, properties-correcting agent 3% (kaolin+water glass+Sodium Silicofluoride 78%, Tai-Ace S 150+potassium aluminium sulfate 9%, calcium hydroxide+calcium chloride 13%) for subsequent use, at first with 97% fluorine gypsum powder, 2% properties-correcting agent is after stirrer fully mixes, the control temperature is at 120 ℃ of lower roasting 2h, naturally cooling, add above-mentioned properties-correcting agent 1%, fully stirring mixes evenly and is finely ground to below the 0.147mm, namely gets modified building fluorine gypsum powder material again.Gained modification fluorgypsum material presetting period 3min, final setting time 6.5min, the folding strength 1.90MPa that measures behind the 24h, ultimate compression strength 7.25MPa.Satisfy " plaster of Paris (GB/T9776-2008) " building gypsum plaster requirement.
Claims (4)
1. one kind is utilized wet fluorgypsum modification to produce the method for building gypsum plaster, it is characterized in that, may further comprise the steps:
1) wet fluorgypsum is removed the free-water of 15-18% through natural air drying or oven dry, and warp is preliminary broken, adds properties-correcting agent and mix in wet fluorgypsum;
The wet fluorgypsum that 2) will add properties-correcting agent carries out low-temperature bake;
3) powder after the roasting is added again properties-correcting agent fully mixes, fine grinding, namely get the modified building plaster powder materials;
The properties-correcting agent total mass per-cent of described wet fluorgypsum mass percent 92-98%, twice adding is 2-8%; The properties-correcting agent consumption of twice adding in front and back is followed successively by 65-85% and the 15-35% of the total consumption of properties-correcting agent; Described properties-correcting agent is one or more and the miscellany of vitriol and calcium containing compound in kaolin, aluminum oxide, water glass, the Sodium Silicofluoride;
The mass ratio of each composition is one or more in kaolin, aluminum oxide, water glass, the Sodium Silicofluoride in the described properties-correcting agent: vitriol: calcium containing compound=1-5:0.1-1:0.1-2;
The described preliminary degree of crushing of step 1) is that particle diameter is not more than 2mm;
Step 2) described maturing temperature is 80-180 ℃, roasting time 1-3h;
The described fine grinding of step 3) is baked powder and properties-correcting agent to be finely ground to particle diameter together be not more than 0.147mm.
2. the wet fluorgypsum modification of the utilization according to claim 1 method of producing building gypsum plaster, it is characterized in that, described vitriol is one or more in Tai-Ace S 150, potassium aluminium sulfate, vitriolate of tartar, the zinc sulfate, and described calcium containing compound is one or more in calcium oxide, calcium hydroxide, the calcium chloride.
3. the wet fluorgypsum modification of the utilization according to claim 1 method of producing building gypsum plaster is characterized in that step 2) described maturing temperature is 100-150 ℃, roasting time is 2h.
4. the wet fluorgypsum modification of the utilization according to claim 3 method of producing building gypsum plaster is characterized in that step 2) kiln that adopts during described roasting is rotary kiln, fluidized-bed or fluidizing furnace.
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Families Citing this family (9)
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RU2566154C1 (en) * | 2014-03-21 | 2015-10-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Ростовский государственный строительный университет" (РГСУ) | Process line for preparing unfired anhydrite binder |
CN105060834B (en) * | 2015-08-11 | 2018-02-27 | 锦洋高新材料股份有限公司 | A kind of fluorgypsum activity cementing material |
CN105923658B (en) * | 2016-04-29 | 2017-09-08 | 湖南省小尹无忌环境能源科技开发有限公司 | A kind of electroplating sludge material utilization method |
CN106758744B (en) * | 2016-12-14 | 2018-06-12 | 郑卫忠 | A kind of integrated bridge and bridge material |
CN107473685B (en) * | 2016-12-19 | 2020-04-17 | 湖南昌迅科技环保股份有限公司 | Fluorgypsum-based plastering material for interior walls and production process thereof |
CN108384283A (en) * | 2018-02-11 | 2018-08-10 | 贵州大学 | A kind of micronization modified method of simple ardealite |
CN113563040A (en) * | 2021-08-16 | 2021-10-29 | 陕西鑫洛建筑节能科技有限公司 | Fluorine gypsum powder, preparation method and prepared gypsum block |
CN114940591A (en) * | 2022-05-10 | 2022-08-26 | 天津拓展伟创材料研究有限公司 | Cementing material for curing high-water-content tailings |
CN115057639A (en) * | 2022-07-26 | 2022-09-16 | 一夫科技股份有限公司 | Method for preparing alpha semi-hydrated gypsum from fluorgypsum |
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CN1569718A (en) * | 2004-05-11 | 2005-01-26 | 武汉理工大学 | Method for source modification treatment of fluoro-gypsum |
CN101121595A (en) * | 2007-07-11 | 2008-02-13 | 湖北中科博策新材料研究院 | Preparation for environmental protection energy-saving building base material by modifying AHF industrial residue-fluorgypsum and technique thereof |
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