CN106007793A - Method for improving frost resistance of excess-sulfate phosphogypsum slag cement product - Google Patents
Method for improving frost resistance of excess-sulfate phosphogypsum slag cement product Download PDFInfo
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- CN106007793A CN106007793A CN201610330143.8A CN201610330143A CN106007793A CN 106007793 A CN106007793 A CN 106007793A CN 201610330143 A CN201610330143 A CN 201610330143A CN 106007793 A CN106007793 A CN 106007793A
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- Prior art keywords
- ardealite
- slag
- goods
- over cure
- cements
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0231—Carbon dioxide hardening
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/28—Mixtures thereof with other inorganic cementitious materials
- C04B11/30—Mixtures thereof with other inorganic cementitious materials with hydraulic cements, e.g. Portland cements
Abstract
The invention belongs to the field of building materials and particularly relates to a method for improving frost resistance of an excess-sulfate phosphogypsum slag cement product. The excess-sulfate phosphogypsum slag cement product is prepared from phosphogypsum, cement clinker powder, slag powder, sand and water. A sulfur-phosphorus gypsum slag cement product is put in an air condition with the concentration of carbon dioxide being 10%-30% to be cured, the internal structure of the product is changed through a carbonization reaction of the sulfur-phosphorus gypsum slag cement product by means of carbon dioxide, a compact structure is obtained, and the frost resistance is improved. The process of the method is simple, high-temperature curing is not required, energy consumption is little, the amount of doped clinker powder is small, the cost is low, secondary pollution cannot be caused, a large quantity of industrial waste slags such as phosphogypsum can be used, and the method has important environmental and economic benefits.
Description
Technical field
The invention belongs to building material field, be specifically related to a kind of method improving over cure ardealite slag cements goods anti-freezing property.
Background technology
Ardealite is the industry byproduct of Wet-process phosphoric acid (WPPA) in phosphorus chemical industry, and it is mainly composed of dihydrate gypsum
(Ca2SO4·2H2O), in usual ardealite, dihydrate gypsum is 85～95%, and containing impurity such as a small amount of phosphorus, fluorine, organic matters,
Its content is relevant with producing rock phosphate in powder composition used.The most annual ardealite by-product amount of China more than 80,000,000 tons, only 20%
Left and right is obtained by, and a large amount of ardealites are stored up as solid waste, and the accumulative ardealite stored up alreadys more than 200,000,000 tons, not only
Occupy a large amount of soil, also result in environmental pollution.Accelerate ardealite recycling, it has also become phosphorus chemical industry sustainable development is anxious
The problem that need to solve.
Over cure ardealite slag cements is with ardealite as primary raw material, adds appropriate slag and Portland clinker powder (or silicon
Acid salt cement) etc. raw material, the Binder Materials of a kind of hydraulicity with higher-strength prepared.Over cure ardealite slag cements
There is intensity high, water-tolerant, the advantages such as sulphate-corrosion resistance is good, can be used in the engineering such as fresh water and sea water.
China is the rarest about the document of over cure ardealite slag cements frost resistance at present, entitled a kind of environment-friendly and energy-efficient coagulation
The patent (200710133461.6) of soil antifreeze discloses a kind of by add rubber powder, magnesium oxide and Alumen and make
This antifreeze is applied in concrete to improve while ensureing the slump frost resistance of concrete by antifreeze agent for concrete, should
Although patent gives a kind of solution strengthening cement frost resistance, but the volume mistake of rubber powder and Alumen in the composition of antifreeze
Greatly, additive volume is high, and cost is high, is unfavorable for promoting on a large scale, and can not be applicable to the cement concrete of all kinds
Goods.Therefore, explore the method promoting over cure ardealite slag cements frost resistance further, there is important actual application value.
Summary of the invention
The purpose of pin of the present invention is to provide a kind of raising over cure ardealite slag cements goods anti-freezing property, the technique that the method relates to
Simply, low cost, prepared over cure ardealite slag cements goods show excellence anti-freezing property, be suitable for popularization and application.
For achieving the above object, the technical solution used in the present invention is:
A kind of method improving over cure ardealite slag cements goods anti-freezing property, comprises the steps: 1) over cure ardealite slag
The preparation of cement products: prepare over cure ardealite slag cements for raw material with ardealite, clinker powder, slag powders, sand and water
Goods；2) carbonized maintaining: by gained over cure ardealite slag cements goods at the air that carbon dioxide volumetric concentration is 10～30%
Under the conditions of carry out carbonized maintaining.
In such scheme, the described carbonized maintaining time is 7～28 days, and the present invention utilizes carbon dioxide and over cure ardealite ore deposit
The entringite that slag cement goods produce in hydration process carries out carbonization, reacts, make calcium in the environment that gypsum content is saturated
Alumen is transformed into calcium aluminate of hydrated carbon, and the bulky grain Gypsum Fibrosum not participating in reaction is wrapped up by the calcium aluminate of hydrated carbon crystal of needle bar shape,
Forming finer and close overall structure, make hydrated product more stable, the intensity of goods increases considerably, and overall performance is changed
It is kind, so that anti-freezing property is greatly increased.
Preferably, the volumetric concentration of described carbon dioxide is 20～30%.
Preferably, before described curing step, prepared over cure ardealite slag cements goods are placed in maintenance 1～14 in air
After it, make entringite that hydration reaction in goods formed and hydrated calcium silicate gel by ardealite particle encapsulation, obtain densification
Body, forms certain intensity；It is subsequently placed in normal-temperature water maintenance 3～14 days, the most significantly rises product strength.
Preferably, in described air, the time of maintenance is 2～3 days.
In such scheme, with ardealite, clinker powder, slag powders for gelling material in described over cure ardealite slag cements goods
Expecting, mass percent shared by each component is: ardealite 32～60%, clinker powder 2～8%, slag powders 38～60%.
Preferably, with ardealite, clinker powder, slag powders as Binder Materials in described over cure ardealite slag cements goods,
Shared by each component, mass percent is: ardealite 40～50%, clinker powder 4～6%, slag powders 45～55%.
In such scheme, in described over cure ardealite slag cements goods, cement mortar rate is 1:(2.5～3.5), water-cement ratio be 1:(2.5～
3)。
In such scheme, described ardealite is the industry byproduct that wet method prepares phosphoric acid, be mainly composed of dihydrate gypsum containing pigment
Shape material.
In such scheme, described clinker powder is formed by Portland clinker grinding or is commercially available portland cement or common
Portland cement, its surface area is more than 360m2/kg。
In such scheme, described slag powders is more than 330m by slag powders grinding to specific surface area2The granular material of/kg.
The invention have the benefit that
1) technique that the present invention relates to is simple, without High Temperature Curing (less energy consumption), chamotte powder (portland cement or common silicic acid
Salt cement) volume is few, low cost, will not produce secondary pollution, and the industrial residues such as ardealite can also be used in a large number, have
Important economy and environmental benefit.
2) the high concentration carbon dioxide process air that the present invention utilizes is simple and easy to get, the waste gas etc. discharged such as thermal power plant, can be big
Amount absorbs and solidified carbon dioxide, reduces the carbon emission in air, beneficially environmental conservation.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, to the present invention
It is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to limit
Determine the present invention.As long as additionally, technical characteristic involved in each embodiment of invention described below is the most not
The conflict of composition just can be mutually combined.
In following example, the reagent used as no specific instructions is commercially available chemical reagent.
In following example, the slag powders that the slag that described slag powders is provided by Wuhan iron and steel joint-stock company is formed through grinding, its ratio
Surface area is 446.3m2/kg；Described P.O 42.5 Portland cement takes from Huaxin Concrete Co., Ltd, specific surface area
For 403.2m2/kg；Hubei Huang Mailing phosphorous chemical industry company limited taken from by ardealite, and moisture content is 22.31%.
Embodiment 1～7
A kind of method improving over cure ardealite slag cements goods anti-freezing property, comprises the following steps:
1) preparation of over cure ardealite slag cements goods: ardealite, slag powders, clinker powder (P.O 42.5 cement) are pressed table
After conditions of mixture ratios mixes described in 1, add normal sand, then by " Test method for strength of hydraulic cement mortar " (ISO method) (GB/T
17671-1999) molding prepares over cure ardealite slag cements mortar specimen；
2) carbonized maintaining: by gained over cure ardealite slag cements mortar specimen maintenance 3 days in atmosphere, be subsequently placed in normal-temperature water
Middle maintenance 14 days, then it is placed in the air atmosphere that carbon dioxide volumetric concentration is 20% continuation maintenance 28 days, then experience 25 freeze thawing
Circulation, tests the intensity of each stage sample, and result is shown in Table 2 respectively.
The formula of table 1 over cure ardealite slag cements goods
| Numbering | Cement mortar rate | Water-cement ratio | Ardealite/% | P.O 42.5 ordinary cements/% | Slag powders/% |
| Embodiment 1 | 1:3 | 1:2.8 | 32 | 4 | 64 |
| Embodiment 2 | 1:3 | 1:2.8 | 40 | 4 | 56 |
| Embodiment 3 | 1:3 | 1:2.8 | 48 | 4 | 48 |
| Embodiment 4 | 1:3 | 1:2.8 | 60 | 4 | 36 |
| Embodiment 5 | 1:3 | 1:2.8 | 45 | 2 | 53 |
| Embodiment 6 | 1:3 | 1:2.8 | 45 | 6 | 49 |
| Embodiment 7 | 1:3 | 1:2.8 | 45 | 8 | 47 |
The intensity under different curing conditions of table 2 over cure ardealite slag cements goods
From the point of view of the intensity level in each maintenance stage in table 2, gained over cure ardealite slag cements goods through carbonized maintaining and
After freeze-thaw cycle, its intensity is all significantly increased, and illustrates that carbonized maintaining process can make the frost resistance of over cure ardealite slag cements obtain
To significantly improving.
Embodiment 8～10
A kind of method improving over cure ardealite slag cements goods anti-freezing property, comprises the following steps:
1) preparation of over cure ardealite slag cements goods: ardealite, slag powders, clinker powder (P.O 42.5 cement) are pressed
After proportioning mixing described in table 3, add normal sand (mortar ratio is 1:3), then by " Test method for strength of hydraulic cement mortar " (ISO
Method) (GB/T 17671-1999) type prepares over cure ardealite slag cements mortar specimen；
2) carbonized maintaining: by gained over cure ardealite slag cements mortar specimen maintenance 3 days in atmosphere, be subsequently placed in normal-temperature water
Middle maintenance 14 days, is placed in carbon dioxide volumetric concentration the most again and is 10～continues maintenance 28 in the air atmosphere of 30% (being shown in Table 4)
My god, then experience 25 freeze-thaw cycle, test the intensity of each stage sample.
The formula of table 3 over cure ardealite slag cements goods
The frost resistance contrast under different gas concentration lwevel curing conditions of the table 4 over cure ardealite slag cements goods
As can be seen from Table 4, gas concentration lwevel is that the frost resistance of the over cure ardealite slag cements goods obtained when 20% is best.
Embodiment 11～13
A kind of method improving over cure ardealite slag cements goods anti-freezing property, comprises the following steps:
1) preparation of over cure ardealite slag cements goods: ardealite, slag powders, clinker powder (P.O 42.5 cement) are pressed table
After conditions of mixture ratios mixes described in 3, add normal sand, then by " Test method for strength of hydraulic cement mortar " (ISO method) (GB/T
17671-1999) molding prepares over cure ardealite slag cements mortar specimen；
2) carbonized maintaining: by gained over cure ardealite slag cements mortar specimen maintenance 3 days in atmosphere, is often then respectively placed in
Maintenance 3 days, 7 days, 14 days in warm water, then it is placed in the air atmosphere that carbon dioxide volumetric concentration is 20% continuation maintenance 28
My god, then experience 25 freeze-thaw cycle, and test the intensity of each stage sample, result is shown in Table 5 respectively.
As can be seen from Table 5, normal-temperature water maintenance natural law is controlled in the range of 3～14 days, by extending normal-temperature water curing time,
Can effectively promote anti-freezing property.
The impact on over cure ardealite slag cements goods frost resistance of the table 5 normal-temperature water curing time
Embodiment 14～17
A kind of method improving over cure ardealite slag cements goods anti-freezing property, comprises the following steps:
1) preparation of over cure ardealite slag cements goods: ardealite, slag powders, clinker powder (P.O 42.5 cement) are pressed
After proportioning mixing described in table 3, add normal sand (mortar ratio is 1:3), then by " Test method for strength of hydraulic cement mortar " (ISO
Method) (GB/T 17671-1999) type prepares over cure ardealite slag cements mortar specimen；
2) carbonized maintaining: by gained over cure ardealite slag cements mortar specimen maintenance 3 days in atmosphere, be subsequently placed in normal-temperature water
Middle maintenance 14 days, is placed in carbon dioxide volumetric concentration the most again and is 10～continues to support respectively in the air atmosphere of 30% (being shown in Table 4)
Protect 14 days, 21 days, 28 days, then experience 25 freeze-thaw cycle, test the intensity of each stage sample, the results are shown in Table 6.
The impact on over cure ardealite slag cements goods frost resistance of table 6 carbonization time
As can be seen from Table 6, by extending carbonization time, the anti-freezing property of sample can effectively be promoted.
Comparative example
Ratio requirement as described in table 2 prepares over cure ardealite slag cements mortar specimen, is the most directly placed in normal-temperature water and supports
Protect 14 days, then experience 25 freeze-thaw cycle, test the intensity of each stage sample, the results are shown in Table 7.
Table 7 over cure ardealite slag cements frost resistance under the conditions of standard curing
The above results shows, carbonization treatment can effectively promote the anti-freezing property of sample, after carbonization treatment, and over cure ardealite slag
The internal structure of cement products is finer and close, and character is more stable, and the performance of anti-freezing property is more excellent, has been more suitably applied to freeze thawing
The occasion of circulation, the such as most area of China northeast, the service life of building can also be improved in these area application,
And then the usage amount of minimizing armored concrete, energy-saving and emission-reduction are significant.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all the spirit and principles in the present invention it
Interior made any amendment, equivalent and improvement etc., should be included within the scope of the present invention.
Claims (10)
1. the method improving over cure ardealite slag cements goods anti-freezing property, it is characterised in that comprise the steps: 1)
The preparation of over cure ardealite slag cements goods: prepare over cure for raw material with ardealite, clinker powder, slag powders, sand and water
Ardealite slag cements goods；2) carbonized maintaining: in carbon dioxide volumetric concentration be by gained over cure ardealite slag cements goods
10～30% air conditions under carry out carbonized maintaining.
Method the most according to claim 1, it is characterised in that the described carbonized maintaining time is 7～28 days.
Method the most according to claim 1, it is characterised in that the volumetric concentration of described carbon dioxide is 20～30%.
Method the most according to claim 1, it is characterised in that before described curing step, by the over cure ardealite ore deposit of preparation
Slag cement goods are placed in air maintenance 1～14 days, are subsequently placed in normal-temperature water maintenance 3～14 days.
Method the most according to claim 4, it is characterised in that in described air, the time of maintenance is 2～3 days.
Method the most according to claim 1, it is characterised in that in described over cure ardealite slag cements goods with ardealite,
Clinker powder, slag powders are Binder Materials, and mass percent shared by each component is: ardealite 32～60%, clinker powder
2～8%, slag powders 38～60%.
Method the most according to claim 1, it is characterised in that in described over cure ardealite slag cements goods with ardealite,
Clinker powder, slag powders are Binder Materials, and mass percent shared by each component is: ardealite 40～50%, clinker powder
4～6%, slag powders 45～55%.
Method the most according to claim 1, it is characterised in that in described over cure ardealite slag cements goods, cement mortar rate
For 1:(2.5～3.5), water-cement ratio is 1:(2.5～3).
Method the most according to claim 1, it is characterised in that described ardealite is the industry byproduct that wet method prepares phosphoric acid,
It is mainly composed of the aqueous granular material of dihydrate gypsum.
Method the most according to claim 1, it is characterised in that described clinker powder is by Portland clinker grinding
Becoming or be commercially available portland cement or Portland cement, its surface area is more than 360m2/kg；Described slag powders is by slag powders
Grinding to specific surface area is more than 330m2The granular material of/kg.
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| CN110002898A (en) * | 2019-03-26 | 2019-07-12 | 山东建筑大学 | A kind of complex building plastering periodicity maintaining process |
| CN111848080A (en) * | 2020-07-09 | 2020-10-30 | 武汉理工大学 | Over-sulfur phosphogypsum slag cement stabilizing layer, phosphogypsum-based cementing material and preparation method thereof |
| CN114956628A (en) * | 2022-05-12 | 2022-08-30 | 昆明理工大学 | High-strength phosphogypsum-based recycled aggregate and preparation method thereof |
| CN115259729A (en) * | 2022-08-19 | 2022-11-01 | 湖北昌耀新材料工程技术研究有限责任公司 | Excessive-sulfur phosphogypsum-slag cementing material modifier, application thereof and excessive-sulfur phosphogypsum-slag cementing material composition |
| CN115385716A (en) * | 2022-08-04 | 2022-11-25 | 西南科技大学 | Baking-free lightweight aggregate and preparation method thereof |
| CN115477483A (en) * | 2022-09-23 | 2022-12-16 | 济南大学 | Carbonization strengthening super-sulfate cement and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115385716A (en) * | 2022-08-04 | 2022-11-25 | 西南科技大学 | Baking-free lightweight aggregate and preparation method thereof |
| CN115259729A (en) * | 2022-08-19 | 2022-11-01 | 湖北昌耀新材料工程技术研究有限责任公司 | Excessive-sulfur phosphogypsum-slag cementing material modifier, application thereof and excessive-sulfur phosphogypsum-slag cementing material composition |
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| CN115477483A (en) * | 2022-09-23 | 2022-12-16 | 济南大学 | Carbonization strengthening super-sulfate cement and preparation method thereof |
| CN115477483B (en) * | 2022-09-23 | 2023-04-25 | 济南大学 | Carbonized reinforced super sulfate cement and preparation method thereof |
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Application publication date: 20161012 |