CN103708747A - Modified phosphogypsum material used for sea reclamation projects - Google Patents
Modified phosphogypsum material used for sea reclamation projects Download PDFInfo
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- CN103708747A CN103708747A CN201310631209.3A CN201310631209A CN103708747A CN 103708747 A CN103708747 A CN 103708747A CN 201310631209 A CN201310631209 A CN 201310631209A CN 103708747 A CN103708747 A CN 103708747A
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- phosphogypsum
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Abstract
The invention discloses a modified phosphogypsum material used for sea reclamation projects. Phosphogypsum modification is realized by raw material selection and proportioning, so that the phosphogypsum can be used for sea reclamation. The materials comprise phosphogypsum and steel slag powder. The modified phosphogypsum material provided by the invention has high fill strength, good water resistance and high compressive strength, not only can meet the compressive strength requirements of road construction and wharf construction, etc., but also can make heavy use of solid wastes in the phosphorus chemical industry so as to solve the constraint bottleneck problem of waste residue utilization during sustainable development of the phosphorus chemical industry, thus promoting comprehensive utilization of the steel slag powder resources and providing the modified phosphogypsum material suitable for sea reclamation.
Description
Technical field
The present invention relates to building material field, relate in particular to a kind of modified ardealite material that can be used for marine reclamation land engineering.
Background technology
Marine reclamation land refers to land is changed into in original marine site, lake region or riverbank.To few coastal cities, the many level lands of Yushan Hill, it is the very effective ways on development manufacture level land, urban district that marine reclamation land is one.Marine reclamation land can increase urban construction and industrial production land used, beautifies shoreline, improves coastal landscape, even brings more land under cultivation, and increases grain yield.Different according to marine reclamation land material therefor, the pattern of reclaiming fields from the sea can be divided into hill excavating and offshore filling, rubbish and fill out sea, extract extra large sand and fill out sea etc.Yet at present marine reclamation land technology exists some shortcomings, as not high enough in the ultimate compression strength of marine reclamation land material, tamp that intensity is not high, stability is bad, cause filler to run off serious, destroyed the whole structure of marine reclamation land.
According to relevant statistics, show, the annual newly-increased phosphogypsum quantity discharged in the whole world reaches 2.8 hundred million tons at present, approximately 5,000 ten thousand tons, China, account for 20% of world's phosphogypsum annual emissions, a large amount of phosphogypsums is stacked, not only land occupation resource, increases tremendous economic burden to enterprise, but also can cause certain pollution to environment.Therefore, accelerate strength of technical renovation, realize the comprehensive utilization of the industrial solid castoffs such as phosphogypsum, radical cure phosphogypsum is stacked the problem in the urgent need to address that the improper pollution causing has become industry Faced In Sustainable Development.According to < < State Council, about printing and distributing the gist of a document of the notice > > (No. [2013] 5, promulgated by the State Council) of Circular Economy Development Strategy and Immediate action plan, one of resource utilization major construction projects have been listed in the comprehensive utilization of phosphogypsum in.The comprehensive utilization of phosphogypsum has become Establishing Circular Economy Syste m in China, one of vital task of building a resource-conserving and environment-friendly society.Yet, because poor water resistance and the intensity of phosphogypsum are not high, and affected by sea washes, and cause it to be unsuitable for marine reclamation land, use.
Steel slag comprises slag and blast-furnace slag, and the by product producing while being Steel Plant's iron and steel smelting is about 30%～40% and 12%～15% of output of steel.Along with the development of China's Iron And Steel Industry, steel slag output also increases year by year.Levigating steel slag is the main path of slag high value recycling as cement mixture and coagulation material adulterant, but because slag activity is lower, the more high reason of preparation cost has restricted applying of steel-making slag powder.
In prior art, phosphogypsum is carried out to modification and make its method of using for marine reclamation land, its curing speed and the effect that can reach are undesirable, and complicated component, easily cause water to pollute, a kind of soil body stabilizing agent as disclosed in CN101544891.Therefore, in prior art, lack a kind of modified ardealite that needs are used in marine reclamation land that is suitable for.
Summary of the invention
The object of the present invention is to provide a kind of modified ardealite material that can be used for marine reclamation land engineering, solved and in prior art, lacked a kind of problem that the modified ardealite of needs is used in marine reclamation land that is suitable for.
Can be used for a modified ardealite material for marine reclamation land engineering, by the raw material of following mass percent, made:
Phosphogypsum 70%～90%, iron and steel ground-slag 10%～30%.
The mass percent of described raw material is:
Phosphogypsum 80%～90%, iron and steel ground-slag 10%～20%.
Described phosphogypsum is the fresh phosphogypsum discharging in Wet-process Phosphoric Acid Production process or the phosphogypsum of storing up.
Described phosphogypsum is in Wet-process Phosphoric Acid Production process, to adopt the fresh phosphogypsum of dry method discharge or the phosphogypsum of storing up.
Described iron and steel ground-slag is any one or several in S95 level, S85 level, S75 level iron and steel ground-slag.
Modified ardealite material of the present invention is for the application of marine reclamation land engineering.
The main component of phosphogypsum is terra alba (CaSO
42H
2o), the content of terra alba is generally more than 70%, separately containing a small amount of phosphoric acid salt and fluoride impurities.The present invention's phosphogypsum used is the fresh phosphogypsum discharging in Wet-process Phosphoric Acid Production process or the phosphogypsum of storing up.The chemical composition sampling analysis result of the phosphogypsum that store up the dry slag of certain phosphogypsum field is as shown in table 1, and fresh phosphogypsum chemical composition sampling analysis result is as shown in table 2.In sampling analysis, find, phosphogypsum is its particle diameter meeting Natural classification in wet row's process, coarse particles (high silicon components) concentrates on top, fine particle sinks to bottom, in wet deslagging field, samples on a small scale, is difficult to accomplish sample particle even thickness, therefore sampling is not representative, and adopt the fresh phosphogypsum of dry method discharge even with the grain thickness of the phosphogypsum of storing up, and be conducive to mix, form comparatively stable.
The main chemical compositions of the fresh phosphogypsum of table 1
| Sequence number | Composition | Component content/% |
| 1 | SO 3 | 39.36 |
| 2 | CaO | 29.04 |
| 3 | SiO 2 | 9.45 |
| 4 | Fe 2O 3 | 0.08 |
| 5 | Al 2O 3 | 0.13 |
| 6 | MgO | 0.02 |
| 7 | P 2O 5 | 1.41 |
| 8 | F | 0.26 |
| 9 | Free-water | 21.5 |
The main chemical compositions of the phosphogypsum that table 2 is stored up
| Sequence number | Composition | Component content/% |
| 1 | SO 3 | 42.11 |
| 2 | CaO | 31.01 |
| 3 | SiO 2 | 9.65 |
| 4 | Fe 2O 3 | 0.07 |
| 5 | Al 2O 3 | 0.20 |
| 6 | MgO | 0.03 |
| 7 | P 2O 5 | 0.96 |
| 8 | F | 0.19 |
| 9 | Free-water | 6.5 |
Marine reclamation land modified ardealite of the present invention is to take phosphogypsum material as matrix, and the iron and steel ground-slag of take combines as reinforcement, and himself can pass through series of physical, chemical action, obtains modified ardealite material; After other marine reclamation land material mixing, pass through together series of physical, chemical action, can become hard solid by slurry, and the materials such as sand, stone, brick can be cemented to whole material, various materials make up for each other's deficiencies and learn from each other in performance, produce synergistic effect, make the over-all properties of composite gelled material be better than the performance of former composition material, and meet marine reclamation land required tamp the requirements such as intensity, high compressive strength.
Phosphogypsum contains the objectionable impuritiess such as a small amount of phosphorus, fluorine and free acid, and long-term accumulation can cause the pollution of earth's surface and underground water, seriously restricts the prodution and development of sulphur dioxide of phosphor chemical industry.The water tolerance of phosphogypsum is poor, therefore, phosphogypsum need modification just can safety for marine reclamation land.The present invention has adopted iron and steel ground-slag and phosphogypsum interaction to reach modified effect, adds iron and steel ground-slag in phosphogypsum, by hydration and sclerization, has improved the water tolerance of modified ardealite material.Iron and steel ground-slag has certain potential gelation activity, and the main component of phosphogypsum is calcium sulfate, is a kind of Sulfates exciting agent.The present invention is the exciting agent performance of utilizing phosphogypsum, and the potential gelation activity of essential mineral phase tricalcium silicate, Dicalcium Phosphate (Feed Grade), calcium aluminoferrite in iron and steel ground-slag is activated, and makes steel-making slag powder possess the character of hydraulic material, thereby forms gel.After iron and steel ground-slag fully mixes with a large amount of phosphogypsums, iron and steel ground-slag react with part phosphogypsum and forms gelling material, the modified ardealite material that the while forms a kind of marine reclamation land with the mode of wrapping up and phosphogypsum.By effective modification of phosphogypsum, not only can give it is suitable for the height that marine reclamation land uses and tamps the speciality such as intensity, high compressive strength, can also, by reacting to each other between material composition for alleviating its infringement of contained harmful substances to environment, solve the modification technology problem for the phosphogypsum of marine reclamation land.
The by product that the present invention's iron and steel ground-slag used produces while being Steel Plant's iron and steel smelting, comprises slag and blast-furnace slag composition, and component content meets relevant criterion.Iron and steel ground-slag can improve singly mixes easy Qinshui, the segregation that slag powders brings coagulation material, utilizes the microdilatancy characteristic of steel-making slag powder to reduce contraction that large slag powder brings coagulation material shortcoming large, easy to crack etc.Iron and steel ground-slag is divided into S95 level, S85 level and S75 level and the iron and steel ground-slag below S75 level by activity index.Wherein, when the activity index of steel-making slag powder volume iron and steel ground-slag 20%～30% time is higher, can reach S95 grade standard; Steel-making slag powder volume iron and steel ground-slag activity index 40%～50% time can reach the requirement of S75 level.Activity index is poor lower than the activity of the iron and steel ground-slag of S75 level.Iron and steel ground-slag can be for engineerings such as marine reclamation lands, but about iron and steel ground-slag, for the formulating of marine reclamation land material, there is not yet report at present.Because the activity of iron and steel ground-slag own is not high, therefore be difficult to effective utilization.The present invention creatively suitably arranges in pairs or groups iron and steel ground-slag and phosphogypsum, and the modified ardealite material obtaining possesses the conditions such as the marine reclamation land needed ultimate compression strength of material, curing speed.Iron and steel ground-slag and phosphogypsum interact, and have certain stimulation effect.In the time of both well-proportioned, better to the modified effect of phosphogypsum.
It is below test example of the present invention.
Test example 1
1.1 impacts of different proportionings on the modified ardealite strength of materials
Under normal curing condition (20 ℃ ± 2 ℃ of temperature, the environment that relative humidity is greater than 90%), carry out the hydration reaction of modified ardealite.Phosphogypsum adopts chemical composition phosphogypsum as shown in table 2, and iron and steel ground-slag adopts the iron and steel ground-slag of S85 level.The proportioning raw materials of group 3 is with embodiment 3, and the proportioning raw materials of group 4 is with embodiment 1.The proportioning raw materials of modified ardealite material is as shown in table 4, and the hydration reaction result under normal curing condition is as shown in table 5.
1.2 test-results
The proportioning raw materials of table 4 modified ardealite material
| Group | Phosphogypsum | Iron and steel ground-slag |
| 1 | 100% | 0 |
| 2 | 90% | 10% |
| 3 | 80% | 20% |
| 4 | 70% | 30% |
The hydration reaction result of the different proportionings of table 5 under normal curing condition
| Group | Presetting period/min | Final setting time/min | 14d ultimate compression strength/MPa |
| 1 | 6 | 22 | 0.8 |
| 2 | 11 | 34 | 0.8 |
| 3 | 19 | 42 | 1.8 |
| 4 | 26 | 50 | 2.8 |
From above-mentioned test, phosphogypsum has very high hydration activity, adds water hydration reaction occurs immediately, generates dihydrate gypsum, condenses simultaneously and hardens, and has certain intensity.The hydrating characteristics of phosphogypsum is that hydration reaction speed is very fast, and general 5～6min left and right starts aquation crystallization, substantially completes hydration reaction in 2h, generates dihydrate gypsum, forms crystalline network hardenite.Yet by test, find, in phosphogypsum, add the iron and steel ground-slag of different ratios to carry out modification, resulting presetting period, final setting time and 14d ultimate compression strength are different.This may be because slow than phosphogypsum of the hydration reaction speed of the slag composition in iron and steel ground-slag, early strength is low, after phosphogypsum hydration reaction finishes substantially, the hydration reaction of slag composition just starts, composition in iron and steel ground-slag and the composition generation comprehensive action in phosphogypsum afterwards, the former hydration reaction progressively carries out, intensity sustainable growth, and intensity level is that between phosphogypsum 70%～90%, iron and steel ground-slag 10%～30%, the increase along with iron and steel ground-slag improves in the two ratio.Visible, the later strength of modified ardealite material is mainly to provide owing to having the composition hydration and hardening of gelling in material.Therefore, proportioning raw materials of the present invention is selected appropriate, can obtain the modified effect that is suitable for marine reclamation land.
Test example 2 water tolerance tests
To than the test specimen of making, enter in water by each assembly in test example 1, at different time, survey intensity, the result obtaining demonstration, best by the water tolerance of group 3, group 4 proportioning gained accessories, the water tolerance of group 1 is the poorest.Visible, when the ratio range of phosphogypsum and iron and steel ground-slag is during at phosphogypsum 70%～90%, iron and steel ground-slag 10%～30%, modified ardealite material has good water tolerance.This may be because, phosphogypsum belongs to air hardening cementitious materials, poor water resistance, but by adding iron and steel ground-slag to carry out after modification, water tolerance is greatly improved, and the prolongation along with soaking time, intensity can further improve, and this may be due to after acquiring a certain degree when iron and steel ground-slag volume, and article construction intensity is mainly that the aquation crystalline texture net by steel slag meal component is provided, and as hydraulic cementing materials, the intensity of iron and steel ground-slag can progressively increase in water.When steel slag powder content is lower than 10% time, the intensity of goods is mainly provided by dihydrate gypsum crystalline texture net, after immersion, because the node of dihydrate gypsum crystalline texture is very easily water-soluble, and cause strength degradation, and the crystalline texture net undercapacity of steel slag meal component is to make up loss of strength, Gu the poor effect of improving to water tolerance.
Beneficial effect of the present invention: there is the higher intensity of tamping, water-tolerant, ultimate compression strength is high, not only can meet the ultimate compression strength requirement such as repair the roads, construct a wharf; Can also utilize in a large number the solid waste of sulphur dioxide of phosphor chemical industry, solve the restriction bottleneck problem of waste residue utilization in sulphur dioxide of phosphor chemical industry process of sustainable development, promoted the comprehensive utilization of iron and steel ground-slag resource and a kind of modified ardealite material that marine reclamation land is used that is suitable for is provided; Because its production cost is lower, more utilize the performance of its Environmental Role.The solid waste that the raw material of the modified ardealite material of marine reclamation land is sulphur dioxide of phosphor chemical industry, belongs to recycling economy technical study, can alleviate the pressure of the solid waste comprehensive utilization in sulphur dioxide of phosphor chemical industry evolution simultaneously; The production process of this material is easy and simple to handle, and 14 days ultimate compression strength of the solid material of formation, at 0.8～2.8MPa, can meet the service requirements of the different purposes after marine reclamation land.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described.The following stated is preferred embodiment of the present invention, can be used for explaining and supporting the present invention, but the present invention is not done to any pro forma restriction, any technical solution of the present invention content that do not depart from, and according to simple modification, equivalent variations and modification that technical spirit of the present invention is done following examples, all still belong in the scope of technical solution of the present invention.
The using method of marine reclamation land modified ardealite material of the present invention: be first the service requirements according to marine reclamation land, select the proportioning raw materials of modified ardealite material and other associated materials; Then corresponding raw material is stirred to marine reclamation land mixture processed.
Embodiment 1
Be phosphogypsum 70% and iron and steel ground-slag 30% feeding by mass percentage, after sending into and stirring in stirrer, then add water and continue to stir; Obtain the modified ardealite material of marine reclamation land.This material ultimate compression strength of 14 days reaches 2.8MPa.Described phosphogypsum is the phosphogypsum of storing up in Wet-process Phosphoric Acid Production process.Described iron and steel ground-slag is S95 level iron and steel ground-slag.
Embodiment 2
Be phosphogypsum 80% and 20% feeding by mass percentage, after sending into and stirring in stirrer, then add water and continue to stir; Obtain the modified ardealite material of marine reclamation land.This material ultimate compression strength of 14 days reaches 1.8MPa.Described iron and steel ground-slag is S85 level iron and steel ground-slag.
Embodiment 3
Be phosphogypsum 90% and iron and steel ground-slag 10% feeding by mass percentage, after sending into and stirring in stirrer, then add water and continue to stir; Obtain the modified ardealite material of marine reclamation land.This material ultimate compression strength of 14 days reaches 0.8MPa.
Embodiment 4～11
According to the method shown in embodiment 1, carry out the preparation of the modified ardealite material of embodiment 4～11, fill a prescription as shown in table 6:
Table 6 embodiment 4～11 formulas
| Embodiment | Phosphogypsum (%) | Iron and steel ground-slag (%) |
| 4 | 72 | 28 |
| 5 | 74 | 26 |
| 6 | 76 | 24 |
| 7 | 78 | 22 |
| 8 | 82 | 18 |
| 9 | 84 | 16 |
| 10 | 86 | 14 |
| 11 | 88 | 12 |
Embodiment 12
Be phosphogypsum 70% and iron and steel ground-slag 30% feeding by mass percentage, after sending into and stirring in stirrer, then add water and continue to stir; Obtain the modified ardealite material of marine reclamation land.This material ultimate compression strength of 14 days reaches 2.8MPa.
Described phosphogypsum is the fresh phosphogypsum that adopts dry method discharge in Wet-process Phosphoric Acid Production process.
Described iron and steel ground-slag is the powder mix of S95 and S85 level iron and steel ground-slag.
Embodiment 13
Be phosphogypsum 70% and iron and steel ground-slag 30% feeding by mass percentage, after sending into and stirring in stirrer, then add water and continue to stir; Obtain the modified ardealite material of marine reclamation land.This material ultimate compression strength of 14 days reaches 2.8MPa.
Described phosphogypsum is the phosphogypsum of storing up that adopts dry method discharge in Wet-process Phosphoric Acid Production process.Described iron and steel ground-slag is S75 level iron and steel ground-slag.
Claims (6)
1. a modified ardealite material that can be used for marine reclamation land engineering, is characterized in that: the raw material by following mass percent is made:
Phosphogypsum 70%～90%, iron and steel ground-slag 10%～30%.
2. a kind of modified ardealite material that can be used for marine reclamation land engineering as claimed in claim 1, is characterized in that: the mass percent of described raw material is:
Phosphogypsum 80%～90%, iron and steel ground-slag 10%～20%.
3. a kind of modified ardealite material that can be used for marine reclamation land engineering as described in as arbitrary in claim 1～2, is characterized in that: described phosphogypsum is the fresh phosphogypsum discharging in Wet-process Phosphoric Acid Production process or the phosphogypsum of storing up.
4. a kind of modified ardealite material that can be used for marine reclamation land engineering as claimed in claim 3, is characterized in that: described phosphogypsum is in Wet-process Phosphoric Acid Production process, to adopt the fresh phosphogypsum of dry method discharge or the phosphogypsum of storing up.
5. a kind of modified ardealite material that can be used for marine reclamation land engineering as claimed in claim 3, is characterized in that: described iron and steel ground-slag is any one or several in S95 level, S85 level, S75 level iron and steel ground-slag.
6. a kind of application that can be used for the modified ardealite material of marine reclamation land engineering as claimed in claim 3, is characterized in that: for the application of marine reclamation land engineering.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104671682A (en) * | 2015-02-02 | 2015-06-03 | 武汉理工大学 | Method for preparing hemihydrate gypsum gel material and gypsum products on line by using phosphogypsum at hot stage |
| CN109369119A (en) * | 2018-10-29 | 2019-02-22 | 程钰 | The preparation and application method of modified ardealite Load materials based on aluminium smelting waste residue |
| CN113292310A (en) * | 2021-06-22 | 2021-08-24 | 河南建筑材料研究设计院有限责任公司 | Gypsum-based heat-insulating slurry and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051719A (en) * | 1990-05-16 | 1991-05-29 | 云南省建筑材料科学研究设计院 | A kind of new phospho-gypsum cementing agent and production method thereof and application |
-
2013
- 2013-12-02 CN CN201310631209.3A patent/CN103708747A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051719A (en) * | 1990-05-16 | 1991-05-29 | 云南省建筑材料科学研究设计院 | A kind of new phospho-gypsum cementing agent and production method thereof and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104671682A (en) * | 2015-02-02 | 2015-06-03 | 武汉理工大学 | Method for preparing hemihydrate gypsum gel material and gypsum products on line by using phosphogypsum at hot stage |
| CN109369119A (en) * | 2018-10-29 | 2019-02-22 | 程钰 | The preparation and application method of modified ardealite Load materials based on aluminium smelting waste residue |
| CN113292310A (en) * | 2021-06-22 | 2021-08-24 | 河南建筑材料研究设计院有限责任公司 | Gypsum-based heat-insulating slurry and preparation method thereof |
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Application publication date: 20140409 |