CN101423350A - Anhydrite cement for building and method for producing the same - Google Patents

Anhydrite cement for building and method for producing the same Download PDF

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Publication number
CN101423350A
CN101423350A CNA2008102341005A CN200810234100A CN101423350A CN 101423350 A CN101423350 A CN 101423350A CN A2008102341005 A CNA2008102341005 A CN A2008102341005A CN 200810234100 A CN200810234100 A CN 200810234100A CN 101423350 A CN101423350 A CN 101423350A
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CN
China
Prior art keywords
anhydrite
cement
volume
building cement
hydraulicity
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.)
Pending
Application number
CNA2008102341005A
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Chinese (zh)
Inventor
唐绍林
万建东
唐修仁
丁大武
刘丽娟
徐红英
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ZHEJIANG EFFUL NEW MATERIAL SCIENCE AND TECHNOLOGY Co Ltd
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ZHEJIANG EFFUL NEW MATERIAL SCIENCE AND TECHNOLOGY Co Ltd
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Publication date
Application filed by ZHEJIANG EFFUL NEW MATERIAL SCIENCE AND TECHNOLOGY Co Ltd filed Critical ZHEJIANG EFFUL NEW MATERIAL SCIENCE AND TECHNOLOGY Co Ltd
Priority to CNA2008102341005A priority Critical patent/CN101423350A/en
Publication of CN101423350A publication Critical patent/CN101423350A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00Calcium sulfate cements
    • C04B11/05Calcium sulfate cements obtaining anhydrite, e.g. Keene's cement
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C04B28/16Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing anhydrite, e.g. Keene's cement
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

Abstract

The invention discloses anhydrite cement for building and a method for producing the same. The anhydrite cement for building comprises anhydrite, catalysts, alkaline excitants, hydraulic admixture and crystal seeds; the added quantities of the components in weight proportion are: 1 to 5 percent of the catalysts, 0 to 10 percent of the alkaline excitants, 0 to 30 percent of the hydraulic admixture, 0 to 3 percent of the crystal seeds, and 50 to 95 percent of the anhydrite; and the components are ground or mixed, the fineness reaches 0.08 square hole sieve, and the triage is less than 10 percent. The anhydrite cement can use phosphogypsum or devulcanized gypsum as a raw material which is calcined into the anhydrite. With the invention, the anhydrite cement with hydraulicity the coefficient of softing of which is more than 0.7, and the 28-day mortar compressive strength of which reaches two labels of 20 MPa and 30 MPa can be prepared, and air hardening keene's cement the softening coefficient of which is less than 0.6 and the 28-day net cement paste compressive strength of which is more than 35 MPa can be prepared.

Description

A kind of anhydrite for building cement and production method thereof
Technical field
The present invention relates to a kind of gelling material for building and production method thereof, relate in particular to a kind of anhydrite for building cement and production method.
Background technology
Natural anhydrous calciumsulphate can be produced anhydrite cement, but because of natural anhydrous calciumsulphate structure tight, the hydration rate super snail, the early hydration rate is lower, the later stage volume stability is poor, can not satisfy service requirements.The way that solves is to improve the powder fineness, increases cost so again and is difficult for accomplishing.
Simultaneously, phosphogypsum and desulfurated plaster all are industrial residues, but they all are good gypsum raw materials.Mostly adopt cryogenic calcining process to produce beta-type semi-hydrated gypsum (being plaster of Paris) at present both at home and abroad, this product strength is lower, and water resistance is poor, and range of application is very limited.The also useful alpha type high-strength gypsum of producing, but yield poorly, the cost height.In addition, the detrimental impurity in the phosphogypsum slag is more, must wash and could use, and gypsum per ton will be with 4~5 tons of water.In China that water resources lacks, this method is worthless.
Summary of the invention
Technical problem solved by the invention provides a kind of anhydrite for building cement and production method.
Technical scheme of the present invention is: a kind of anhydrite for building cement comprises dehydrated gyp-, catalyzer, alkali-activator and hydraulicity blended material and crystal seed; By weight ratio, wherein the volume of catalyzer is 1~5%, and the volume of alkali-activator is 0~10%, and the volume of hydraulicity blended material is 0~32%, and the volume of crystal seed is 0~3%, and the volume of dehydrated gyp-is 50~95%; Above-mentioned component is carried out mix grinding or mixing, and fineness reaches 0.08 square hole sieve and tails over less than 10%.
Described dehydrated gyp-is that industrial by-product phosphogypsum or flue gas desulfurization gypsum form through calcining, and calcining temperature is 500 0~800 0C.As preferred version of the present invention, described calcining temperature is preferably 600 0~700 0C.
Being contained in more than 80% of dihydrate gypsum in the described phosphogypsum, water ratio is below 20%; Dihydrate gypsum content is more than 80% in the described desulfurated plaster, and water ratio is below 20%.
Described catalyzer is vitriol or potassium bichromate, and pure chemistry material volume is preferably in 1~3%, and the alunite ore can be given birth to usefulness, also can be 800 0C uses the calcining back down, and volume is preferably in 2~5%.
Described alkali-activator is to contain the material that generates calcium hydroxide after calcium hydroxide or the aquation, and its volume is preferably in 3~10%.
Described hydraulicity blended material is the material that can generate hydrated calcium silicate or aquation calcium sulphoaluminate after the aquation.
Described crystal seed is dihydrate gypsum or semi-hydrated gypsum.
A kind of anhydrite for building Cement Production method, with the catalyzer that is 1~5% by weight ratio, 0~10% alkali-activator, 0~32% hydraulicity blended material, 0~3% crystal seed and 50~95% dehydrated gyp-carry out mix grinding or mixing, and fineness reaches 0.08 square hole sieve and tails over less than 10%.
The present invention adopts high-temperature calcination technology in order to overcome the deficiencies in the prior art, and phosphogypsum or desulphurization gypsum calcination are become II type dehydrated gyp-, is mixed with anhydrite cement again.At this moment phosphogypsum and desulfurated plaster are not all wanted pre-treatment and are directly used.Objectionable impurities in the phosphogypsum is not burnt, and changes into insoluble inert substance exactly.And the water resistance of anhydrite cement improves range of application expansion greatly.Mix a certain amount of catalyzer or alkali-activator, make its presetting period greater than 40 minutes, final setting time was less than 12 hours.In order to improve the water resistance of anhydrite cement, also mix blended material, as blast furnace slag, water quenching phosphorus slag, flyash etc. with hydraulicity.Also mix the dihydrate gypsum crystal seed, preferably mix semi-hydrated gypsum and improve catalytic effect.Adopt technical solution of the present invention, can be mixed with and have the hydraulicity, coefficient of softening reached the anhydrite cement of 20Mpa, two labels of 30Mpa greater than 0.7,28 day mortar ultimate compression strength, with coefficient of softening less than 0.6 air-setting keene's cement, clean slurry was done ultimate compression strength greater than 35MPa in 28 days.
Embodiment
The present invention uses rotary kiln 500 to phosphogypsum or desulfurated plaster 0~800 0Calcine in the C scope, preferably be controlled at 600 0~700 0In the C scope, at this moment the II type dehydrated gyp-of Sheng Chenging has stronger activity.The hydration and hardening speed of II type dehydrated gyp-is slower, in order to satisfy normal service requirements, mixes a certain amount of catalyzer or alkali-activator, makes its presetting period greater than 40 minutes, and final setting time was less than 12 hours.In order to improve the water resistance of anhydrite cement, also to mix blended material, as blast furnace slag, water quenching phosphorus slag, flyash etc. with hydraulicity.In order to improve catalytic effect, also can mix the dihydrate gypsum crystal seed, preferably mix semi-hydrated gypsum, generate dihydrate gypsum after the aquation.Above-mentioned all materials carry out mix grinding or mixing after measuring by proportioning.Wherein mix grinding is to be added to together after all material is measured in proportion to carry out grinding in the milling equipment, and fineness requirement reaches the 0.08mm square hole sieve and tails over less than 10%; Mixing be with all material in advance grinding tail over fineness to the 0.08mm square hole sieve less than 10%, be added to together after the metering in proportion again and be blended in pulverizer in the mixing equipment and be crushed to fineness and reach the 0.08mm square hole sieve and tail over less than 10%.Because the hardness of slag, phosphorus slag etc. is bigger, difficult mill; And the low easily mill of anhydrite hardness, so together can be inhomogeneous during grinding, coarse grain must be a slag class material.In order to make various materials can both reach same fineness, preferably adopt various materials difference grindings after same fineness, mix by the proportioning metering again.
Wherein phosphogypsum is the waste residue of phosphate fertilizer plant discharging, being contained in more than 80% of its dihydrate gypsum, and water ratio is below 20%; To be the coal-burning power plant carry out the waste residue that produces when desulfurization is handled to flue gas to desulfurated plaster, and its dihydrate gypsum content is more than 80%, and water ratio is below 20%.These two kinds of waste residues all do not need pre-treatment just can directly use.
Most of vitriol all can be used as catalyzer, as vitriolate of tartar, sodium sulfate, sodium pyrosulfate, alum with contain the alunite etc. of vitriol, also having potassium bichromate also is good catalyzer, and pure chemistry material volume is 1~3%, the alunite ore can be given birth to usefulness, also can be 800 0C uses the calcining back down, and volume is 2~5%.
Contain the material that generates calcium hydroxide after calcium hydroxide or the aquation and all can be used as alkali-activator and use, as unslaked lime, slaked lime, carbide slag and silicate cement etc.
The material that can generate hydrated calcium silicate or aquation calcium sulphoaluminate after all aquations all can be used as hydraulicity blended material and uses, as blast furnace slag, water quenching phosphorus slag, slag, flyash, volcanic ash etc.
Specify anhydrite cement with the form of form below and the air-setting keene's cement cooperates examples of properties when.
Wherein the anhydrite cement cement mortar strength is measured by international GB/T 17671-1999 " Test method for strength of hydraulic cement mortar ".Use the 1:3 mortar, but test specimen is measured intensity under the 450C drying condition.
(1) 1:3 mortar ultimate compression strength is greater than 30.0Mpa, and coefficient of softening is greater than 0.8 proportioning.
Example Dehydrated gyp-% Catalyzer % Exciting agent % Crystal seed % Blended material % Ultimate compression strength MPA Remarks
1 (phosphogypsum) 55 (alunite) 3.5 (saltcake) 0.5 (cement) 8 Semi-hydrated gypsum 3 Slag 30 37.0 Mix
2 (phosphogypsum) 57 (alunite) 4 (unslaked lime) 6 Semi-hydrated gypsum 3 Slag 30 31.0 Mix
3 (phosphogypsum) 60 (alunite) 4 (vitriolate of tartar) 1 (cement) 8 0 Slag 28 33.2 Mix
4 (desulfurated plaster) 55 (alunite) 3 (cement) 8 Semi-hydrated gypsum 3 Slag 30 38.5 Mix
5 (desulfurated plaster) 57 (alunite) 4 (unslaked lime) 6 Semi-hydrated gypsum 3 Slag 30 32.5 Mix
6 (phosphogypsum) 55 (alunite) 4 (NaHS0 4)0.5 (slaked lime) 10 Semi-hydrated gypsum 0.5 Slag 30 32.7 Mix
Annotate: 1, phosphogypsum and desulfurated plaster are 650 0Burn till dehydrated gyp-under the C temperature.
2, alunite is 800 0Burn till under the C temperature.
3, cement is 52.5 neat portland cements.
(2) 1:3 mortar ultimate compression strength is greater than 20.0Mpa, and coefficient of softening is greater than 0.7 proportioning.
Annotate: 1, phosphogypsum and desulfurated plaster are 550 0Burn till dehydrated gyp-under the C temperature.
2, not calcining of alunite.
3, cement is 42.5 ordinary Portland cements.
(3) air-setting keene's cement (cement) proportioning, coefficient of softening is less than 0.6.
Example Dehydrated gyp-% Catalyzer % Exciting agent % Crystal seed % Clean slurry is done ultimate compression strength MPA
13 (desulfurated plaster 500 0C burns till) 92 Alum 2 Unslaked lime 3 Semi-hydrated gypsum 3 40.5
14 (desulfurated plaster 600 0C burns till) 95 NaHSO 4?2 Unslaked lime 3 Semi-hydrated gypsum 0 36.2
15 (phosphogypsum 700 0C burns till) 94 K 2SO 4?3 0 Semi-hydrated gypsum 3 41.1
16 (phosphogypsum 800 0C burns till) 95 K 2SO 4?1? Na 2SO 4?1 0 Semi-hydrated gypsum 3 36.5
17 (phosphogypsum 650 0C burns till) 89 Alunite 3 Unslaked lime 5 Semi-hydrated gypsum 3 40.2
Annotate: 1, the anhydrite cement of air-setting generally claims keene's cement.

Claims (9)

1, a kind of anhydrite for building cement is characterized in that: comprise dehydrated gyp-, catalyzer, alkali-activator and hydraulicity blended material and crystal seed; By weight ratio, wherein the volume of catalyzer is 1~5%, and the volume of alkali-activator is 0~10%, and the volume of hydraulicity blended material is 0~32%, and the volume of crystal seed is 0~3%, and the volume of dehydrated gyp-is 50~95%; Above-mentioned component is carried out mix grinding or mixing, and fineness reaches 0.08 square hole sieve and tails over less than 10%.
2, anhydrite for building cement according to claim 1 is characterized in that: described dehydrated gyp-is that industrial by-product phosphogypsum or flue gas desulfurization gypsum form through calcining, and calcining temperature is 500 °~800 ℃.
3, anhydrite for building cement according to claim 2 is characterized in that: described calcining temperature is preferably 600 °~700 ℃.
4, anhydrite for building cement according to claim 2 is characterized in that: being contained in more than 80% of dihydrate gypsum in the described phosphogypsum, and water ratio is below 20%; Dihydrate gypsum content is more than 80% in the described desulfurated plaster, and water ratio is below 20%.
5, anhydrite for building cement according to claim 1, it is characterized in that: described catalyzer is vitriol or potassium bichromate, and pure chemistry material volume is preferably in 1~3%, and the alunite ore can be given birth to usefulness, also can be 800 ℃ of calcining back uses down, volume is preferably in 2~5%.
6, anhydrite for building cement according to claim 1 is characterized in that: described alkali-activator is to contain the material that generates calcium hydroxide after calcium hydroxide or the aquation, and its volume is preferably in 3~10%.
7, anhydrite for building cement according to claim 1 is characterized in that: described hydraulicity blended material is the material that can generate hydrated calcium silicate or aquation calcium sulphoaluminate after the aquation.
8, anhydrite for building cement according to claim 1 is characterized in that: described crystal seed is dihydrate gypsum or semi-hydrated gypsum.
9, the described anhydrite for building Cement Production of a kind of claim 1 method, it is characterized in that: will be 1~5% catalyzer by weight ratio, 0~10% alkali-activator, 0~30% hydraulicity blended material, 0~3% crystal seed and 50~95% dehydrated gyp-carry out mix grinding or mixing, and fineness reaches 0.08 square hole sieve and tails over less than 10%.
CNA2008102341005A 2008-11-21 2008-11-21 Anhydrite cement for building and method for producing the same Pending CN101423350A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684675B (en) * 2009-08-19 2012-01-11 四川宏达股份有限公司 Autoclaved phosphogypsum brick and method for preparing same
CN102491662A (en) * 2011-11-25 2012-06-13 安徽省皖北煤电集团有限责任公司含山恒泰非金属材料分公司 Natural anhydrous gypsum-made bonding material
CN103408278A (en) * 2013-08-19 2013-11-27 四川省建材工业科学研究院 Method for preparing anhydrite cementing slurry with ardealite
CN104496236A (en) * 2015-01-06 2015-04-08 荆门盛隆科技有限公司 Binding material gypsum-based ecological cement and production method thereof
CN105482504A (en) * 2015-11-29 2016-04-13 贵州开磷集团股份有限公司 Method for preparing PVC filling material from phosphogypsum as raw material
CN110054468A (en) * 2019-05-27 2019-07-26 兰溪市绘歆工艺品有限公司 A kind of method of plastering surface growth crystallization
CN110128045A (en) * 2019-04-30 2019-08-16 江苏一夫科技股份有限公司 II type anhydrous gypsum fast hydration exciting agent of one kind and fast hydration method

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684675B (en) * 2009-08-19 2012-01-11 四川宏达股份有限公司 Autoclaved phosphogypsum brick and method for preparing same
CN102491662A (en) * 2011-11-25 2012-06-13 安徽省皖北煤电集团有限责任公司含山恒泰非金属材料分公司 Natural anhydrous gypsum-made bonding material
CN102491662B (en) * 2011-11-25 2013-04-17 安徽省皖北煤电集团有限责任公司含山恒泰非金属材料分公司 Natural anhydrous gypsum-made bonding material
CN103408278A (en) * 2013-08-19 2013-11-27 四川省建材工业科学研究院 Method for preparing anhydrite cementing slurry with ardealite
CN103408278B (en) * 2013-08-19 2015-02-04 四川省建材工业科学研究院 Method for preparing anhydrite cementing slurry with ardealite
CN104496236A (en) * 2015-01-06 2015-04-08 荆门盛隆科技有限公司 Binding material gypsum-based ecological cement and production method thereof
CN105482504A (en) * 2015-11-29 2016-04-13 贵州开磷集团股份有限公司 Method for preparing PVC filling material from phosphogypsum as raw material
CN110128045A (en) * 2019-04-30 2019-08-16 江苏一夫科技股份有限公司 II type anhydrous gypsum fast hydration exciting agent of one kind and fast hydration method
CN110054468A (en) * 2019-05-27 2019-07-26 兰溪市绘歆工艺品有限公司 A kind of method of plastering surface growth crystallization
CN110054468B (en) * 2019-05-27 2021-05-14 兰溪市绘歆工艺品有限公司 Method for growing crystals on surface of gypsum product

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Open date: 20090506