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 PDF

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Publication number
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
wet
properties
correcting agent
building gypsum
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CN 201110026571
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CN102173620A (en
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郭朝晖
肖细元
周康根
张康
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Central South University
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Central South University
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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

A kind of method of utilizing wet fluorgypsum modification production building gypsum plaster
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.
CN 201110026571 2011-01-25 2011-01-25 Method for modifying and producing building gypsum powder by utilizing wet fluorgypsum Expired - Fee Related CN102173620B (en)

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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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