CN108675751A - A kind of environment-friendly type mud composite curing agent - Google Patents

A kind of environment-friendly type mud composite curing agent Download PDF

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Publication number
CN108675751A
CN108675751A CN201810514240.1A CN201810514240A CN108675751A CN 108675751 A CN108675751 A CN 108675751A CN 201810514240 A CN201810514240 A CN 201810514240A CN 108675751 A CN108675751 A CN 108675751A
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China
Prior art keywords
slag
curing agent
environment
friendly type
mud
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CN201810514240.1A
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Chinese (zh)
Inventor
王东星
胡旭
伍林峰
高向雲
杜怡莹
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Wuhan University WHU
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Wuhan University WHU
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Priority to CN201810514240.1A priority Critical patent/CN108675751A/en
Publication of CN108675751A publication Critical patent/CN108675751A/en
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    • 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
    • C04B28/30Compositions 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 magnesium cements or similar cements
    • C04B28/32Magnesium oxychloride cements, e.g. Sorel 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00767Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
    • C04B2111/00784Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes for disposal only
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The invention discloses a kind of environment-friendly type mud composite curing agents, including following dry powder raw material:Slag or slag composition, carbide slag, Na2SO4, magnesia, magnesium chloride, silica flour and Sodium Polyacrylate;Wherein slag composition is the mixture of the mixture or slag and the mixture or slag of slag, flyash and slag of slag and flyash.Curing agent prepared by the present invention, mud is difficult to the stable technical problem that is cured in the case of solving high-moisture percentage, and after addition accounts for the curing agent of mud dry weight 35%, 70% intensity of moisture content mud 7 days can reach 4.0Mpa or more;The present invention makes full use of trade waste flyash, silica flour, carbide slag, slag, Steel-slag to replace the cured mode of conventional cement base, effectively reduces energy consumption and CO2Discharge, while the materials such as chlorine oxygen magnesium of novel green added help to improve early stage and later strength and the stability of drilling mud makes it easy to transport or reach engineering under the premise of meeting economic and environment-friendly and fills requirement.

Description

A kind of environment-friendly type mud composite curing agent
Technical field
The present invention relates to a kind of environment-friendly type mud composite curing agent, the waste sludge suitable for oil drilling, geological drilling Curing process is starched, civil construction Material Field is belonged to.
Background technology
When drillng operation, well drilling waste mud has the characteristics that larger dosage, complex chemical composition, type are more, therefore It is extremely difficult when handling well drilling waste mud, the measure taken now to these mud is more, but from economic benefit Consider, only have sub-fraction and be recycled, the overwhelming majority be directly discharged in environment, or take natural evaporation, It precipitates, consolidate, being buried in the measures progress simply and easy treat such as neighbouring.About 200~3,000,000 m are discharged in China every year according to statistics3Waste sludge Slurry, wherein being directly discharged to account for 1/3 in environment.These mud clay contents are high, intensity is low, stack and occupy large amount of land resources, Transportation cost is high and is difficult to directly be utilized by engineering.Therefore discarded slurry innoxious process for treating is studied and applies, for protection Regional environment realizes that human kind sustainable development has very important significance.
Existing slurry curing processing mainly realizes its consolidation using materials such as cement, lime, vitreum or pitches. It is that Free water becomes combining water in hole, and reinforces bonding between particle that hydration reaction, which occurs, by pore water and curing materials Power increases intensity.But in practical applications, the hardening of the condensation of materials such as ordinary cement, lime is slow, when moisture content is more than 1.0 times of liquid limits Or when higher, it is difficult to make mud reach design strength or need additive amount very big, and may be used also in the case of high water-solid ratio Non-condensing the phenomenon that just part settles can occur.It is very unreasonable from the aspect of project cost.The present invention is abandoning tradition Cement-based solidified material on the basis of be added to new additive agent, can moisture content be higher than 1.0 times of liquid limits in the case of meet Solidifying requirements reach some strength.
Granulated blast-furnace slag (abbreviation slag) is byproduct when being smelted in 1350 DEG C -1550 DEG C of blast furnace, glass Body content is up to 95% or more.Be not used, land occupation resource while is also a kind of waste of resource, ingredient with it is general Logical Portland cement is similar, and price is only the half of cement.But this material hydration rate is slow, in certain circumstances Its activity can be excited.Carbide slag is the waste residue generated when producing important industrial chemicals acetylene with calcium carbide, main component Ca (OH)2、CaCO3、SiO2, sulfide, inorganic matters and a small amount of organic matter such as metal oxides, the hydroxide such as magnesium and iron.
Invention content
The purpose of the present invention is intended to big for conventional curing agents dosage and the features such as be difficult to handle moisture content high mud, carries Go out a kind of environment-friendly type mud composite curing agent environmental-friendly and of reasonable cost.While high-moisture percentage mud is effectively treated, Discarded slurry is changed into resource on a large scale, reduces the dosages such as cement, lime, high degree reduces project cost.
A kind of environment-friendly type mud composite curing agent, which is characterized in that include following dry powder raw material by weight percentage:
Slag or slag composition:40%-50%;
Carbide slag:6-18%;
Na2SO4:5%-12%;
Magnesia:10-20%;
Magnesium chloride;4-10%;
Silica flour:3%-12%;
Sodium Polyacrylate:0.1%-0.4%;
The slag composition is the mixture of slag and flyash, and mass ratio is 3~2:1;Or slag and slag is mixed Object is closed, mass ratio is 3~2:1;Or the mixture of slag, flyash and slag, mass ratio 5:2:3 or 5:3:2.
Above-mentioned environment-friendly type mud composite curing agent, the dry powder raw material fineness are 300m2/kg-600m2/kg。
Above-mentioned environment-friendly type mud composite curing agent, the flyash are high-calcium fly ass, CaO content >=10%.
Above-mentioned environment-friendly type mud composite curing agent, the slag grain size are less than 2mm.
Above-mentioned environment-friendly type mud composite curing agent, MgO >=90% in the magnesia dry powder.
Above-mentioned environment-friendly type mud composite curing agent, Ca (OH) in the carbide slag2Content >=85%.
Above-mentioned environment-friendly type mud composite curing agent, the silica flour are high activity silica flour, SiO2Content >=90%.
Above-mentioned environment-friendly type mud composite curing agent, the Sodium Polyacrylate are super absorbent resin, and absorb water ratio 1:500.
Above-mentioned environment-friendly type mud composite curing agent, the Na2SO4For high-purity dry powder, wherein Na2SO4Content >=99%.
Environment-friendly type mud composite curing agent of the present invention, compared with prior art advantage be:
(1) dry powder such as abundant recycling industrial waste material slag, carbide slag, silica flour, and selectively add work Industry obsolete material flyash and/or slag, and new material super absorbent resin is introduced, environment-friendly type mud composite solid is prepared with this Agent, this method are of low cost and simple for process convenient to carry out.
(2) present invention has the characteristics that aquation, hardening are fast, is consumed by the generation of the hydration reaction and entringite of material The physics water sorption of a large amount of free waters and Sodium Polyacrylate, absorbs rapidly a large amount of free moistures from mud.Therefore in height Particle sedimentation can occur before to avoid condensation in the case of water-solid ratio.It can be directly used for processing moisture content and be higher than one times of liquid limit Above mud.
(3) be added account for the curing agent of mud dry weight 35% after, 70% intensity of moisture content mud 7 days can reach 4.0Mpa with On.
(4) curing materials that the present invention uses are environmental-friendly, while stablizing conducive to the solidification of mud, and early strength is with after Phase intensity is secure.
(5) when curing to certain sludge containing heavy metal ion, the slag in curing agent has it certain absorption Effect, and part heavy metal ion can be also wrapped in fine and close spacial framework in material bonding process, reach Reduce the purpose of heavy metal ion exudation concentration.
The preparation method of environment-friendly type mud composite curing agent of the present invention is:According to each raw material proportioning of composite curing agent, divide Also known as take slag, carbide slag, Na2SO4, magnesia, magnesium chloride, the dry powder such as silica flour, by above-mentioned raw materials combined grinding to specific surface area 300m2/kg-600m2/ kg is mixed with Sodium Polyacrylate again, both obtains mud composite curing agent.
High-moisture percentage mud composite curing agent disclosed by the invention, technical principle are:When slag is contacted with water, only A small amount of Ca2+In plasma diffusing W,Mo to solution, and the alumino-silicate protected acidic film prevention slag of a break calcium is formed in slag surface Further aquation, but carbide slag hydrolysis generates a large amount of OH-Ion, slag overcome the decomposition activation energy of rich calcium phase in such circumstances, It abolishes and is previously generated protected acidic film, and continue deeper into Si-rich phase, the SiO that vitreous structure disintegration generates4 4-、AlO4 5-、 Ca2+Ion enters solution and reconfigures to form new hydrated product.And the unstable silica four of fine coal gray surface in such circumstances Face body (SiO4 4-) and Al3+Instead of Si4+Aluminum-oxygen tetrahedron (the AlO of formation4 5-) gradually it is corrupted such that vitreous structure disintegrates, Many silicates and aluminate ion are formed in fine coal gray surface, a large amount of Ca generated with slag aquation2+Ion occurs instead at this time Hydrated calcium silicate or drated calcium aluminate should be formed.Tricalcium silicate, dicalcium silicate in slag with hydraulic gelling etc. are simultaneously Take part in the heat evolution velocity of hydration reaction and the slag of promotion.Na2SO4Addition provide SO4 2-, promote the generation of entringite And stabilization.
In addition to this large amount of Ca in solution2+Ion can displace the low order K on clay particle surface+、Na+Ion, due to Ca2+Ions binding moisture film is thin, causes the combination moisture film for the crumb structure that clay particle is combined into also relatively thin, to clay particle Between attract each other reunionizations occur, repulsion reduction, cohesive strength so that soil structures are even closer between particle.
Magnesium chloride is reacted as conditioning agent with magnesia in water generates basic magnesium chloride, consumes a large amount of free waters in mud While make its hardening so that its intensity constantly increases.
Main component is SiO2Silica flour pozzolanic activity it is big, respond is strong in alkaline solution.With surplus in environment Mg2+Ion reacts producible MgSiO3Floccule, at the same also with Ca (OH)2Reaction generates CaSiO3Precipitation blocks hardening Capillary channel in body reduces Ca in solution2+With Mg2+Concentration.Constantly consumption Ca (OH)2Slag hydration rate is accelerated again. In addition to this, the specific surface area of silica flour is very big, can adsorb a large amount of Free waters and can play filling effect with flyash.
Sodium Polyacrylate can quickly in absorbent slurry moisture, and be constantly in water conservation state, be present in aquation Stable state is formed among the spatial skeleton that product is formed.
Specific implementation mode
Below by embodiment, the present invention is further explained.
Embodiment 1
A kind of environment-friendly type mud composite curing agent, including following components, each component are become by dry powder quality percentage group:
Slag:30%;
Flyash:10%;
Carbide slag:15%;
Magnesia:15%;
Sodium Polyacrylate:0.2%;
Silica flour:8%;
Magnesium chloride:10%
Na2SO4:11.8%.
According to the environment-friendly type mud composite curing agent that this proportioning configures, 200kg curing agent is mixed in every cubic metre of mud, Mud initial aqueous rate is set as 70%, after mud and curing agent uniform stirring, prepares diameter 50mm, height 100mm samples, Standard curing demoulds after 1 day, and continues maintenance to 7 days and 28 days, and each age is carried out anti-without lateral spacing using three parallel samples Compressive Strength.Curing sludge can reach 3.64MPa in 7 days curing age mean intensities, and curing age mean intensity can reach within 28 days 7.97MPa。
Embodiment 2
A kind of environment-friendly type mud composite curing agent, including following components, each component are become by dry powder quality percentage group:
Slag:35%;
Slag:10%;
Magnesia:12%
Carbide slag:18%;
Sodium Polyacrylate:0.1%;
Silica flour:12%;
Magnesium chloride:5%
Na2SO4:7.9%.
According to the environment-friendly type mud composite curing agent that this proportioning configures, 200kg curing agent is mixed in every cubic metre of mud, Mud initial aqueous rate is set as 70%, after mud and curing agent uniform stirring, prepares diameter 50mm, height 100mm samples, Standard curing demoulds after 1 day, and continues maintenance to 7 days and 28 days, and each age is carried out anti-without lateral spacing using three parallel samples Compressive Strength.Curing sludge can reach 4.31MPa in 7 days curing age mean intensities, and curing age mean intensity can reach within 28 days 8.27MPa。
Embodiment 3
A kind of environment-friendly type mud composite curing agent, including following components, each component are become by dry powder quality percentage group:
Slag:25%;
Flyash:15%;
Slag:10%;
Carbide slag:15%;
Magnesia:15%;
Sodium Polyacrylate:0.2%;
Silica flour:6%;
Magnesium chloride:4%
Na2SO4:9.8%.
According to the environment-friendly type mud composite curing agent that this proportioning configures, 200kg curing agent is mixed in every cubic metre of mud, Mud initial aqueous rate is set as 70%, after mud and curing agent uniform stirring, prepares diameter 50mm, height 100mm samples, Standard curing demoulds after 1 day, and continues maintenance to 7 days and 28 days, and each age is carried out anti-without lateral spacing using three parallel samples Compressive Strength.Curing sludge can reach 3.22MPa in 7 days curing age mean intensities, and curing age mean intensity can reach within 28 days 6.35MPa。
Embodiment 4
A kind of environment-friendly type mud composite curing agent, including following components, each component are become by dry powder quality percentage group:
Slag:40%;
Carbide slag:18%;
Magnesia:15%;
Sodium Polyacrylate:0.2%;
Silica flour:8%;
Magnesium chloride:8%
Na2SO4:10.8%.
According to the environment-friendly type mud composite curing agent that this proportioning configures, 200kg curing agent is mixed in every cubic metre of mud, Mud initial aqueous rate is set as 70%, after mud and curing agent uniform stirring, prepares diameter 50mm, height 100mm samples, Standard curing demoulds after 1 day, and continues maintenance to 7 days and 28 days, and each age is carried out anti-without lateral spacing using three parallel samples Compressive Strength.Curing sludge can reach 4.88MPa in 7 days curing age mean intensities, and curing age mean intensity can reach within 28 days 8.84MPa。

Claims (9)

1. a kind of environment-friendly type mud composite curing agent, which is characterized in that include following dry powder raw material by weight percentage:
Slag or slag composition:40%-50%;
Carbide slag:6-18%;
Na2SO4:5%-12%;
Magnesia:10-20%;
Magnesium chloride;4-10%;
Silica flour:3%-12%;
Sodium Polyacrylate:0.1%-0.4%;
The slag composition is the mixture of slag and flyash, and mass ratio is 3~2:1;Or the mixture of slag and slag, Mass ratio is 3~2:1;Or the mixture of slag, flyash and slag, mass ratio 5:2:3 or 5:3:2.
2. environment-friendly type mud composite curing agent according to claim 1, it is characterised in that:
The dry powder raw material fineness is 300m2/kg-600m2/kg。
3. environment-friendly type mud composite curing agent according to claim 1, it is characterised in that:
The flyash is high-calcium fly ass, CaO content >=10%.
4. environment-friendly type mud composite curing agent according to claim 1, it is characterised in that:
The slag grain size is less than 2mm.
5. environment-friendly type mud composite curing agent according to claim 1, it is characterised in that:
MgO >=90% in the magnesia dry powder.
6. environment-friendly type mud composite curing agent according to claim 1, it is characterised in that:
Ca (OH) in the carbide slag2Content >=85%.
7. environment-friendly type mud composite curing agent according to claim 1, it is characterised in that:
The silica flour is high activity silica flour, SiO2Content >=90%.
8. environment-friendly type mud composite curing agent according to claim 1, it is characterised in that:
The Sodium Polyacrylate is super absorbent resin, and absorb water ratio 1:500.
9. environment-friendly type mud composite curing agent according to claim 1, it is characterised in that:
The Na2SO4For high-purity dry powder, wherein Na2SO4Content >=99%.
CN201810514240.1A 2018-05-25 2018-05-25 A kind of environment-friendly type mud composite curing agent Pending CN108675751A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110117143A (en) * 2019-05-10 2019-08-13 大成科创基础建设股份有限公司 A kind of method of magnesium-based composite material solidified slip
CN110218073A (en) * 2019-05-21 2019-09-10 武汉大学 Dredging silt dehydrating and curing calcium and magnesium based composites and the preparation method and application thereof
CN111423080A (en) * 2020-03-02 2020-07-17 南京市城市建设投资控股(集团)有限责任公司 Foundation excavation slurry stabilizing and curing agent and preparation and use method thereof
CN111943625A (en) * 2020-08-21 2020-11-17 河南省交通规划设计研究院股份有限公司 Soft soil curing agent
CN112321262A (en) * 2020-09-25 2021-02-05 中交第二航务工程局有限公司 Low-alkalinity environment-friendly curing agent for river and lake dredging bottom mud and use method thereof
CN113214835A (en) * 2021-06-16 2021-08-06 中国电建集团华东勘测设计研究院有限公司 Soil curing agent for roadbed filling
CN114086539A (en) * 2021-11-24 2022-02-25 安徽理工大学环境友好材料与职业健康研究院(芜湖) Equipment and method for in-situ curing of building waste slurry
CN114349467A (en) * 2022-01-14 2022-04-15 武汉理工大学 Sludge curing agent using magnesia cement and preparation method thereof

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110117143A (en) * 2019-05-10 2019-08-13 大成科创基础建设股份有限公司 A kind of method of magnesium-based composite material solidified slip
CN110117143B (en) * 2019-05-10 2021-09-17 大成科创基础建设股份有限公司 Method for curing slurry by using magnesium-based composite material
CN110218073A (en) * 2019-05-21 2019-09-10 武汉大学 Dredging silt dehydrating and curing calcium and magnesium based composites and the preparation method and application thereof
CN111423080A (en) * 2020-03-02 2020-07-17 南京市城市建设投资控股(集团)有限责任公司 Foundation excavation slurry stabilizing and curing agent and preparation and use method thereof
CN111423080B (en) * 2020-03-02 2022-09-16 南京市城市建设投资控股(集团)有限责任公司 Foundation excavation slurry stabilizing and curing agent and preparation and use method thereof
CN111943625A (en) * 2020-08-21 2020-11-17 河南省交通规划设计研究院股份有限公司 Soft soil curing agent
CN112321262A (en) * 2020-09-25 2021-02-05 中交第二航务工程局有限公司 Low-alkalinity environment-friendly curing agent for river and lake dredging bottom mud and use method thereof
CN112321262B (en) * 2020-09-25 2022-05-06 中交第二航务工程局有限公司 Use method of low-alkalinity environment-friendly curing agent for river and lake dredging bottom mud
CN113214835A (en) * 2021-06-16 2021-08-06 中国电建集团华东勘测设计研究院有限公司 Soil curing agent for roadbed filling
CN114086539A (en) * 2021-11-24 2022-02-25 安徽理工大学环境友好材料与职业健康研究院(芜湖) Equipment and method for in-situ curing of building waste slurry
CN114349467A (en) * 2022-01-14 2022-04-15 武汉理工大学 Sludge curing agent using magnesia cement and preparation method thereof

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