CN1493650A - High cement paste solidifying agent - Google Patents
High cement paste solidifying agent Download PDFInfo
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- CN1493650A CN1493650A CNA031283330A CN03128333A CN1493650A CN 1493650 A CN1493650 A CN 1493650A CN A031283330 A CNA031283330 A CN A031283330A CN 03128333 A CN03128333 A CN 03128333A CN 1493650 A CN1493650 A CN 1493650A
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- solidifying agent
- cement slurry
- dehydrated gyp
- mud
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Abstract
A high-cement-grout solidifying agent for the sludge or silt with 100-350% of water content is prepared from thioaluminate cement clinker, cube spar and calcium lime through proportionally mixing and grinding. Its advantages are quick solidifying and hardening, and high strength.
Description
Technical field:
The present invention relates to a kind of high cement slurry solidifying agent, be applicable to discarded slurry in petroleum drilling, the geological drilling, and the solidification treatment of bottom sludge such as reservoir, water channel, the pool, weir, pond, civil construction material field belonged to.
Background technology:
High cement slurry is water content is flow state much larger than its liquid limit a cohesive soil, for example slurries are discarded in oil field or mine, after mud such as farmland, rivers and creeks, channel, pond and industrial effluent, city domestic sewage are flowed to rivers and lakes, bay, the mud that grogs of fouling product forms at the bottom of the connate water gradually etc.High cement slurry can be considered mainly that (0.002～0.074mm) formation, absolute water content is roughly in 150%～500% scope by minimum clay mineral grain (0.002mm is following) and a small amount of silt particle.The solidification treatment of this class mud is to the regeneration of soil and improve the ecological environment significant.The treatment process of this class mud mainly contains desilting substitution method, Pressure water discharging method, drying and dehydrating method, heat-agglomerating method and chemical consolidation method etc., and the present invention relates generally to the chemical consolidation method.
To the high cement slurry consolidation process, adopt existing solidifying agent such as cement, lime etc., following effect is roughly arranged: the one, the Ca (OH) that emits when utilizing CaO in the unslaked lime and hydrated cementitious
2Carry out ion-exchange with the alkali in the clay mineral, ξDian Wei is reduced, help the soil particle coagulation sedimentation.The 2nd, to absorb moisture when unslaked lime and hydrated cementitious, make the mud retrogradation.The 3rd, the hydrated product that forms when unslaked lime and hydrated cementitious has pectisation, soil particle cementation can be got up.But when practical application, because Portland cement, lime setting and harden are slow, they had the part sedimentation before will occurring not condensing under the high water-solid ratio situation, and contain more organic substance in mud and the mud usually, these organic substances can hinder the hydration reaction of cement, cause the cement organic cohesive soil that can not effectively bond, so the solidification effect of high cement slurry is often very poor even can't carry out.When using lime to solidify, solidification intensity is lower.
Summary of the invention:
The objective of the invention is to: a kind of high cement slurry solidifying agent is provided, high cement slurry or mud are carried out efficient solidification treatment, can not only unlikelyly environment be worked the mischief because of loss the objectionable impurities in mud or the mud is fixed, and can be on a large scale, change discarded slurry or mud into resource at low cost, with mud or mud on-the-spot disposal, backfill utilization.
Purpose of the present invention is achieved through the following technical solutions; A kind of high cement slurry solidifying agent is characterized in that described solidifying agent is made up of sulphoaluminate cement clinker, dehydrated gyp-and unslaked lime, and its compositing range (quality) is:
Dehydrated gyp-25%～45%
With the above-mentioned raw materials combined grinding to specific surface area 300～600m
2/ kg, or with above-mentioned raw materials respectively grinding to specific surface area 300～600m
2Remix is mixed thoroughly behind/the kg.
Aforesaid high cement slurry solidifying agent is characterized in that Wingdale in addition, and its compositing range (quality) is:
Dehydrated gyp-25%～40%
Wingdale 1%～10%.
The best compositing range of above-mentioned raw materials (quality) is:
Dehydrated gyp-30%～36%
Wingdale 3%～5%
Best specific surface area behind the above-mentioned raw materials grinding is 350～400m
2/ kg.
Above-mentioned sulphoaluminate cement clinker is commercially available making with rotary kiln or shaft kiln calcination.Above-mentioned dehydrated gyp-is commercially available natural anhydrite, produce fluorine Lyons waste residue fluorgypsum or through 600 ℃～900 ℃ calcining dihydrate gypsum gained dehydrated gyp-s, wherein fluorgypsum is that left waste residue behind fluorine Lyons is extracted in 500 ℃～800 ℃ reactions of heating of fluorite and sulfuric acid, main component is a calcium sulfate, and a small amount of unreacted fluorite and sulfuric acid.
The present invention is described in detail as follows:
The essential mineral of sulphoaluminate cement clinker is 3CACaSO
4, β-C
2S and C
2As shown in Figure 1 chemical reaction, mainly take place with dehydrated gyp-, unslaked lime and Wingdale acting in conjunction in AS:
Chemical reaction shown in Figure 1 shows the effect of following several respects when solidified slip:
(1) 3CACaSO
4Aquation forms suction, the expansion of ettringite: above chemical equation shows that the mineral hydration reaction in the solidifying agent all can be drawn the moisture, particularly 3CACaSO in the mud morely
4Mineral, owing to form the ettringite contain 32 crystal water, water regain reaches 75.6%, thereby makes a large amount of free water change the water of constitution of ettringite into, makes livering and gelling.Because 3CACaSO
4Hydration and hardening is fast, and therefore, high cement slurry is the multiviscosisty gelatinized by flowing state transition just at short notice.The increase of ettringite solid volume then will inevitably be filled the hole of mass of soil intergranular, makes the solidified mud body become closely knit, plays " it is fine and close to expand " effect.
(2) C
2S and C
2The AS aquation forms the cementation of C-S-H: because the sulphoaluminate cement clinker firing temperature is lower, burn till C at 1250～1350 ℃
2S forms at low temperatures, so it is active higher, can form the C-S-H gel earlier, it not only has the ability of good binder soil particle, and by self high specific surface area, can make being in contact with one another to count out and increasing of particle in the cured body, therefore can provide certain intensity for the slurry curing body.In addition, C
2AS is at gypsum and Ca (OH)
2Effect down also will form ettringite mutually and the C-S-H gel, thereby intensity and expansion all can obtain increase.
(3) ion exchange: high cement slurry is under above-mentioned hydration reaction effect, and water content sharply descends, simultaneously Ca
2+With the ion-exchange of grogs ξDian Wei is descended, mud body by dispersion system to the granule transformation;
(4) fine acicular ettringite, tabular Ca (OH)
2And the tight adhesion of C-S-H gel, cross-lapping become the three-dimensional space rack, be the main source of slurry curing body early strength: the main hydration products of solidifying agent is an acicular calcium aluminite crystal, when its tight adhesion and cross coupled together the time, just constitute a crystalline framework, and C-S-H gel, the tabular Ca of six sides (OH)
2Crystal and AH
3Gel then is filled in the middle of the ettringite.Along with the carrying out of hydration reaction, will form a firm three-dimensional space crystallization spatial grid structure that soil is played enhancement in the solidified slip.Because aquation can produce ettringite rapidly in early days, thereby improve early strength.Along with the growth and the stretching, extension of ettringite needle-like crystal, after it inserts the slit of granule, play the enhancement of a kind of " miniature reinforcement " again.
(5) grogs is at alkali-activator Ca (OH)
2With sulphate activation agent CaSO
4Acting in conjunction under, pozzolanic reaction takes place form C-S-H gel and swelling property ettringite, help the enhancement of later strength and the raising of water stability.
From above-mentioned reaction and the mechanism of action as can be seen, key of the present invention is to allocate an amount of dehydrated gyp-and unslaked lime in sulphoaluminate cement clinker into.Gypsum has many types, different sorts gypsum dissolution speed difference is very big, and semi-hydrated gypsum and dihydrate gypsum dissolving are fast, and they all can reach corresponding degree of supersaturation in the 5min in pure water or in lime solution, but no longer change later on, and solubleness reduces with the increase of lime solution concentration.And the dissolving of dehydrated gyp-s such as anhydrite, fluorgypsum or bassanite is very slow, progressively stripping in water or in the lime solution, and be not subjected to Ca in the solution (OH)
2Even the influence that exists is at Ca (OH)
2In the saturated solution, its last solubleness still may be greater than the solubleness of dihydrate gypsum in pure water.Therefore,,, make ettringite (still under plastic state) formation before setting and harden in large quantities, then do not reach the expansible effect then because the gypsum stripping is too fast if adopt semi-hydrated gypsum or dihydrate gypsum.And the dissolution rate of dehydrated gyp-s such as anhydrite, fluorgypsum or bassanite and characteristics are suitable for sulphoaluminate cement clinker and progressively form ettringite in the setting and harden process of solidified slip, produce the expansible requirement.In addition, the formation of ettringite and the basicity in the liquid phase have confidential relation.When its at saturated Ca (OH)
2In the solution, ettringite mainly provides volumetric expansion near the agglomerating growth of original mineral phase surface, and is favourable for filling pore; When its at unsaturated Ca (OH)
2In the solution, ettringite generates in away from the liquid phase of original mineral and separates out, and is discrete distribution, and the growth that intersects forms spatial grid structure, mainly intensity is worked.General wish have enough expansions to come filling pore in early days solidifying, the later stage then will be avoided the intensive expansion and causes the inside configuration local stress and cause strength degradation when structural strength forms after.For reaching this purpose, just regulate by lime, make it at the curing initial stage, guarantee Ca (OH) in the liquid phase
2Can be saturated, the later stage along with lime by the pozzolanic reaction consumption of clay mineral, Ca in the liquid phase (OH)
2Concentration constantly descends.So lime intermingled quantity is unsuitable too high, but will not reach enough liquid phase basicity very little the time, clay mineral is disintegrated and with Ca (OH)
2Pozzolanic reaction takes place.The effect of Wingdale is that it can participate in 3CACaSO on the one hand
4Aquation, it can also stablize trithiophenol salt type ettringite phase on the other hand, prevents that the trithiophenol salt type ettringite from transforming to single sulphur type ettringite, but if Wingdale mixes too much and will reduce solidification intensity.
Hence one can see that, has only when cooperating with suitable ratio between aluminosulfate cement, dehydrated gyp-, unslaked lime and the Wingdale, just can make its solidified mud obtain the ideal effect.
Major advantage of the present invention shows:
(1) the high cement slurry solidifying agent coagulate soon, fast hard, when sclerosis, can also produce large volume and expand, help improving the structure density and strengthen grogs and connect, therefore have early strong, high-strength characteristics.Under equal conditions, the high cement slurry solidifying agent solidifies the php slurry of water content 200%, be 20～90min its time of coagulation, and 42.5 silicate cements need just can condense at 120～360min, and the high cement slurry solidifying agent improves 1.5～2 times than 42.5 ordinary Portland cement solidified mud hardenite intensity simultaneously.
(2) high cement slurry solidifying agent aquation, sclerosis are soon, by taking place, chemical reaction from mud, absorbs the water of constitution that a large amount of free water contents change into hydrated product, therefore particulate sedimentation phenomenon before can avoiding under the high water-solid ratio condensing can be directly used in and solidify water content up to 100%～350% mud or mud.
(3) influenced by organic matter little for the hydration reaction of high cement slurry solidifying agent, and the organic soil that can bond also has good solidification effect to containing organic high cement slurry and mud.
(4) the strength development temperature influence of high cement slurry solidifying agent is less, also can construct under the lower temperature in the winter time, and temperature all can carry out normal construction more than 0 ℃.
(5) raw material of high cement slurry solidifying agent comprises that sulphoaluminate cement clinker all can directly buy from the market, and can utilize cheap unslaked lime, Wingdale and industrial residue fluorgypsum, so cost is reduced greatly; Produce solidifying agent and only use milling equipment, need not calcine, so it is technology is simple, easy to implement.
(6) the high cement slurry solidifying agent is the single component powdered material, and is therefore easy to use, at the construction field (site) solidifying agent joined to stir in mud or the mud by predetermined proportion to get final product fast setting.
(7) high cement slurry solidifying agent solidified mud or mud both can harden in air, also can harden in water.The mud or the sludge solidification body chemical resistance of concrete that reach certain intensity are good, even be subjected to seawater to do wet immersion effect, cured body does not ftracture, and intensity does not descend yet.
Description of drawings
Fig. 1, the hydration reaction of high cement slurry solidifying agent.
Fig. 2 has listed and has implemented used starting material chemical ingredients.
Fig. 3, the quality proportioning embodiment of high cement slurry solidifying agent.
Fig. 4, high cement slurry solidifying agent and silicate cement are to the curing performance contrast of mud.
Fig. 5, high cement slurry solidifying agent volume, mud moisture content and slurry curing body intensity.
Embodiment:
Fig. 1 is the hydration reaction of high cement slurry solidifying agent.Fig. 2 has listed and has implemented used starting material chemical ingredients.
Fig. 3 is the quality proportioning embodiment of high cement slurry solidifying agent.Fig. 3 has listed the proportioning and the curing performance thereof of high cement slurry solidifying agent.Wherein: used solidifying agent adopts combined grinding to form specific surface area 370m
2/ kg: treat that solidified mud is certain oilfield waste mud, water ratio 200%; The solidifying agent volume is 20% (in quality of mud fluid), injects 70.7 * 70.7 * 70.7mm after stirring with mud
3The cubes die trial places 20 ± 2 ℃ of temperature, and the curing room of relative humidity more than 90% carries out maintenance, and the demoulding behind the 2d continues maintenance after the demoulding, to stipulating to measure slurry curing body unconfined compression strength the length of time.
Fig. 4 has listed the high cement slurry solidifying agent and 42.5 Portland clinkers contrast the curing performance with a kind of mud, and the specific surface area of solidifying agent is 375m
2/ kg.Treat that solidified oilfield waste mud moisture content is 200%, solidifying agent volume 20%.
Fig. 5 has listed the unconfined compression strength that the high cement slurry solidifying agent solidifies same oilfield waste mud with different volumes, and the unconfined compression strength that adopts the high cement slurry solidifying agent to be cured to the oilfield waste mud of different water cut rate.The proportioning of used solidifying agent is a sulphoaluminate cement clinker: fluorgypsum: unslaked lime: Wingdale=58: 31: 7.5: 3.5, and specific surface area 375m
2/ kg.
Claims (5)
1, a kind of high cement slurry solidifying agent is characterized in that described solidifying agent is made up of sulphoaluminate cement clinker, dehydrated gyp-and unslaked lime, and its compositing range (quality) is:
Sulphoaluminate cement clinker 40%～72%
Dehydrated gyp-25%～45%
Unslaked lime 3%～20%
With the above-mentioned raw materials combined grinding to specific surface area 300～600m
2/ kg, or with above-mentioned raw materials respectively grinding to specific surface area 300～600m
2Remix is mixed thoroughly behind/the kg.
2, according to claims 1 described high cement slurry solidifying agent, it is characterized in that Wingdale in addition, its compositing range (quality) is:
Sulphoaluminate cement clinker 40%～71%
Dehydrated gyp-25%～40%
Unslaked lime 3%～12%
Wingdale 1%～10%
3,, it is characterized in that the best compositing range of described raw material (quality) is according to claims 2 described high cement slurry solidifying agent:
Sulphoaluminate cement clinker 50%～60%
Dehydrated gyp-30%～36%
Unslaked lime 7%～9%
Wingdale 3%～5%
Best specific surface area behind the above-mentioned raw materials grinding is 350～400m
2/ kg.
4,, it is characterized in that used sulphoaluminate cement clinker is commercially available making with rotary kiln or shaft kiln calcination according to claims 1,2 described high cement slurry solidifying agent.
5,, it is characterized in that used dehydrated gyp-is commercially available natural anhydrite, produces fluorine Lyons waste residue fluorgypsum or through 600 ℃～900 ℃ calcining dihydrate gypsum gained dehydrated gyp-s according to claims 1,2 described high cement slurry solidifying agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031283330A CN1493650A (en) | 2003-07-17 | 2003-07-17 | High cement paste solidifying agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031283330A CN1493650A (en) | 2003-07-17 | 2003-07-17 | High cement paste solidifying agent |
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| Publication Number | Publication Date |
|---|---|
| CN1493650A true CN1493650A (en) | 2004-05-05 |
Family
ID=34239722
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| CNA031283330A Pending CN1493650A (en) | 2003-07-17 | 2003-07-17 | High cement paste solidifying agent |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358816C (en) * | 2005-11-22 | 2008-01-02 | 刘茂平 | Solidified agent for drilling well waste mud |
| CN101607811B (en) * | 2009-07-16 | 2011-01-05 | 温州大学 | Slurry curing formula |
| CN101941828A (en) * | 2010-08-31 | 2011-01-12 | 中铁四局集团有限公司 | Mud curing agent |
| CN101962256A (en) * | 2010-10-25 | 2011-02-02 | 南京华廷环保科技开发有限公司 | Comprehensive treatment method for blue-green algae sludge |
| CN102211917A (en) * | 2011-03-29 | 2011-10-12 | 湖南科技大学 | High water-containing mud curing agent for mine filling and using method thereof |
| CN102381778A (en) * | 2011-08-30 | 2012-03-21 | 北京恩瑞达科技有限公司 | Method for harmless treatment of drilling well waste mud |
| CN102491720A (en) * | 2011-12-07 | 2012-06-13 | 济南大学 | Curing agent for cement-based rapid-hardening high-moisture discarded mud |
| CN105670641A (en) * | 2016-02-11 | 2016-06-15 | 孙华平 | Soil curing agent for water conservancy dam and preparation method of soil curing agent |
| CN103275730B (en) * | 2013-06-13 | 2017-05-10 | 成都理工大学 | Barium-containing sulphoaluminate soft soil curing agent and preparation method thereof |
| CN108117358A (en) * | 2017-12-29 | 2018-06-05 | 福建建工建材科技开发有限公司 | A kind of curing of waste soil combined processing |
| CN109053101A (en) * | 2018-10-12 | 2018-12-21 | 江苏科技大学 | The construction method of modified sewage sludge and preparation method thereof as well as cover soil material |
| CN110240458A (en) * | 2019-07-04 | 2019-09-17 | 安徽固维特材料科技有限公司 | A kind of tailing solidifying agent for low temperature environment and preparation method thereof, application method |
| CN110386805A (en) * | 2019-08-22 | 2019-10-29 | 大连海事大学 | A kind of new sulfur aluminate-base mud/soft soil curing agent and its application method |
| CN110761263A (en) * | 2019-10-12 | 2020-02-07 | 林艳芬 | Method for reinforcing soft foundation |
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2003
- 2003-07-17 CN CNA031283330A patent/CN1493650A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358816C (en) * | 2005-11-22 | 2008-01-02 | 刘茂平 | Solidified agent for drilling well waste mud |
| CN101607811B (en) * | 2009-07-16 | 2011-01-05 | 温州大学 | Slurry curing formula |
| CN101941828A (en) * | 2010-08-31 | 2011-01-12 | 中铁四局集团有限公司 | Mud curing agent |
| CN101941828B (en) * | 2010-08-31 | 2014-02-12 | 中铁四局集团有限公司 | Mud curing agent |
| CN101962256A (en) * | 2010-10-25 | 2011-02-02 | 南京华廷环保科技开发有限公司 | Comprehensive treatment method for blue-green algae sludge |
| CN101962256B (en) * | 2010-10-25 | 2011-12-14 | 南京华廷环保科技开发有限公司 | Comprehensive treatment method for blue-green algae sludge |
| CN102211917B (en) * | 2011-03-29 | 2012-10-03 | 湖南科技大学 | High water-containing mud curing agent for mine filling and using method thereof |
| CN102211917A (en) * | 2011-03-29 | 2011-10-12 | 湖南科技大学 | High water-containing mud curing agent for mine filling and using method thereof |
| CN102381778B (en) * | 2011-08-30 | 2014-08-20 | 北京恩瑞达科技有限公司 | Method for harmless treatment of drilling well waste mud |
| CN102381778A (en) * | 2011-08-30 | 2012-03-21 | 北京恩瑞达科技有限公司 | Method for harmless treatment of drilling well waste mud |
| CN102491720A (en) * | 2011-12-07 | 2012-06-13 | 济南大学 | Curing agent for cement-based rapid-hardening high-moisture discarded mud |
| CN103275730B (en) * | 2013-06-13 | 2017-05-10 | 成都理工大学 | Barium-containing sulphoaluminate soft soil curing agent and preparation method thereof |
| CN105670641A (en) * | 2016-02-11 | 2016-06-15 | 孙华平 | Soil curing agent for water conservancy dam and preparation method of soil curing agent |
| CN108117358B (en) * | 2017-12-29 | 2020-10-27 | 福建建工建材科技开发有限公司 | Curing method for waste soil composite treatment |
| CN108117358A (en) * | 2017-12-29 | 2018-06-05 | 福建建工建材科技开发有限公司 | A kind of curing of waste soil combined processing |
| CN109053101A (en) * | 2018-10-12 | 2018-12-21 | 江苏科技大学 | The construction method of modified sewage sludge and preparation method thereof as well as cover soil material |
| CN109053101B (en) * | 2018-10-12 | 2021-06-18 | 江苏科技大学 | Modified sludge, preparation method thereof and construction method of modified sludge as soil covering material |
| CN110240458A (en) * | 2019-07-04 | 2019-09-17 | 安徽固维特材料科技有限公司 | A kind of tailing solidifying agent for low temperature environment and preparation method thereof, application method |
| CN110240458B (en) * | 2019-07-04 | 2021-07-16 | 安徽固维特材料科技有限公司 | Tailing curing agent for low-temperature environment and preparation method and use method thereof |
| CN110386805A (en) * | 2019-08-22 | 2019-10-29 | 大连海事大学 | A kind of new sulfur aluminate-base mud/soft soil curing agent and its application method |
| CN110386805B (en) * | 2019-08-22 | 2022-04-01 | 大连海事大学 | Novel sulphoaluminate-based sludge/soft soil curing agent and use method thereof |
| CN110761263A (en) * | 2019-10-12 | 2020-02-07 | 林艳芬 | Method for reinforcing soft foundation |
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