CN107502313A - Spacetabs type fluid loss agent and preparation method and application are used in a kind of seawater well cementation - Google Patents
Spacetabs type fluid loss agent and preparation method and application are used in a kind of seawater well cementation Download PDFInfo
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Abstract
The invention discloses a kind of seawater well cementation spacetabs type fluid loss agent and preparation method and application, prepares：Monomer and initiator for reaction, obtain quaternary anionic copolymer；Monomer is by the methyl propane sulfonic acid of 2 acrylamide 2, unsaturated carboxylic acid, acrylic amide material, allyl polyglycol composition；It is solution A with mixed nitrate deionized water solution；It is B solution with sodium mixture deionized water solution；N2Under protection, A, B solution are instilled in deionized water simultaneously respectively and reacted, obtains calcium aluminium profiles houghite；It is C solution with quaternary anionic copolymer deionized water solution；It is D dispersion liquids with calcium aluminium profiles houghite deionized water dispersion liquid；In N2Protection, by C solution and D dispersion liquid hybrid reactions, obtain seawater well cementation spacetabs type fluid loss agent.Preparation method of the present invention is simple, can significantly improve fluid loss agent control filtration effect, have lasting dispersibility to cement mortar.
Description
Technical field
The present invention relates to a kind of seawater well cementation spacetabs type fluid loss agent and preparation method and application, belongs to reinforcing oil well drop and loses
Aqua field.
Background technology
Can be adopted in inland and offshore oil, in the case that Yi Cailiang is increasingly exhausted, In Oil Field Exploration And Development to ocean and
Develop in terms of deep-well.But because the part metals cationic polyelectrolyte in seawater can influence the rheological characteristic of cement mortar, so that
Fluid loss agent is obtained to decline to a great extent in performances such as control leak-off, scattered and early strengths.Therefore seawater cementing requirements fluid loss agent is having
Have scattered and early powerful while having good drop dehydration effect concurrently.
In order to solve problems, the method generally used has and hydrated cementitious granular absorption to introduce in the polymer
The stronger carboxyl of effect, the sulfonic acid group low to cation sensitivity and the long side chain radical with compared with severely sterically inhibition effect
Group.But this analog copolymer still have two it is obvious the shortcomings that：The introducing of carboxyl is improving Polymer adsorption amount to protect first
While card control dehydration performance, there is stronger deferred action for cement mortar, so that the early strength of slurry declines；
Secondly, regulation and control of the long side-chain radical for the early flow of slurry are more outstanding, but entering with cement mortar hydration reaction
OK, additive is gradually consumed, and so as to be difficult to regulate and control the fluidity in slurry later stage, therefore, it is difficult to meet whole well cementing process pair
In the requirement of cement mortar dispersiveness.
In view of the above-mentioned problems, prepare spacetabs type on calcium aluminium profiles houghite and polyanionic additive intercalation in recent years
The report of additive gradually causes the concern of researcher.This aspect be because calcium aluminium profiles houghite crystal structure with
Single sulfur type aluminum calcium salt in hydrolysis product of cement is very much like, therefore its crystal seed acts on, and may advantageously facilitate cement early water
Change, so as to strengthen slurry early strength；On the other hand, the mode of action of spacetabs type additive is similar to delay and is added dropwise, Ji Jiangchuan
The mode that system additive disposably adds is changed into gradually to be released slowly into cement mortar from neatly stone veneer or between laminate,
Thus greatly improve effective utilization of additive so that the control dehydration of additive and fluidity keep effect to rise.Such as
J.Plank etc. successfully prepares spacetabs type dispersant using phenol/formaldehyde condensation polymer and calcium aluminium profiles houghite intercalation, so as to
Improve the mobility of slurry within the relatively long time, so as to improve the practical efficiency of additive.It is but current known
The preparation of spacetabs type additive although achieve certain progress, but still have deficiency, be mainly manifested in：The research of synthesis is main
Spacetabs type dispersant is concentrated on, the synthesis for spacetabs type fluid loss agent is but rarely reported；On the other hand, at present outside spacetabs type
Add agent to be applied to fresh water cement mortar, the investigation to its seawater performance is less more.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided spacetabs type fluid loss agent is used in a kind of seawater well cementation.
Second object of the present invention is to provide a kind of preparation method of seawater well cementation spacetabs type fluid loss agent.
Third object of the present invention is to provide a kind of application of seawater well cementation spacetabs type fluid loss agent.
Technical scheme is summarized as follows：
The seawater well cementation preparation method of spacetabs type fluid loss agent, comprises the following steps：
(1) take monomer 20-30g to be dissolved in 110mL deionized waters, stirred under normal temperature, adjust the pH=4-7 of solution；
The initiator for accounting for monomer gross mass 0.4%-0.8% is added, at 60-80 DEG C, lower reaction 2-6h is stirred, is cooled to room temperature, obtains
Quaternary anionic copolymer；The monomer is by 2- acrylamide-2-methyl propane sulfonic 76%-82%, unsaturation by quality
Carboxylic acid 3%-5%, acrylic amide material 14%-16%, allyl polyglycol 1%-3% composition；
(2) take 25-40g mixed nitrate to be dissolved in 100mL deionized waters, be made into solution A；The mixed nitrate is
By mol ratio 1-3：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition；10-20g sodium mixture is taken to be dissolved in 100mL
In deionized water, B solution is made into；It by mol ratio is 1-2 that the sodium mixture, which is,：1 NaOH and NaNO3Composition；In N2Protection
Under the conditions of, solution A, B solution are added dropwise in 250ml deionized waters simultaneously respectively, 70-90 DEG C of stirring 24-48 hour, solid-liquid
Separation, solid are dried, and grinding or crushing, obtain calcium aluminium profiles houghite；
(3) 3-6g quaternary anionic copolymer is dissolved in the deionized water boiled of 10 mass times and obtains C solution；Will
1-2g calcium aluminium profiles houghite, which is scattered in the deionized water boiled of 10 mass times, obtains D dispersion liquids；In N2Protect, C is molten
Liquid and the mixing of D dispersion liquids, under the conditions of rotating speed is 200-500 revs/min, react 24-48h at 90-100 DEG C；Separation of solid and liquid, wash
Wash, solid vacuum freeze-drying, grinding or crushing, obtain seawater well cementation spacetabs type fluid loss agent.
Initiator is ammonium persulfate, potassium peroxydisulfate or azo-bis-isobutyrate hydrochloride.
Unsaturated carboxylic acid is maleic acid, acrylic acid and itaconic acid.
Acrylic amide material is acrylamide or N, N- DMAA.
The number-average molecular weight of allyl polyglycol is 600-1200.
Step (1) reaction time is preferably 4h.
Preferably, mixed nitrate is by mol ratio 2：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition.
Preferably, sodium mixture be by mol ratio be 2：1 NaOH and NaNO3Composition.
Spacetabs type fluid loss agent is used in seawater well cementation prepared by the above method.
The application that above-mentioned seawater well cementation is cemented the well with spacetabs type fluid loss agent seawater.
Advantages of the present invention：
(1) for the present invention using water as solvent, preparation method is simple, easily realizes industrialized production.
(2) spacetabs type fluid loss agent is used in seawater of the invention well cementation, because its slow-release function avoids hydrogen-oxygen in cement mortar
Change co-precipitation interference of the materials such as magnesium for additive, so as to improve the actual adsorbance between additive and cement granules, because
This can significantly improve the control filtration effect of fluid loss agent.
(3) spacetabs type fluid loss agent is used in seawater of the invention well cementation, the anionic between its calcium aluminium profiles houghite laminate
Copolymer by the way that anion exchange reaction occurs so as to realize slow-release function with the anion that is formed in cement mortar hydration process,
Thus there is more lasting dispersibility to cement mortar.
(4) the seawater of the invention well cementation crystal structure of calcium aluminium profiles houghite and cement water in spacetabs type fluid loss agent
The single sulfur type aluminum calcium salt changed in product is very much like, therefore its crystal seed acts on, and may advantageously facilitate cement early hydration, so as to
Alleviate the cement mortar caused by unsaturated carboxyl in polyanion additive and cross retardation phenomenon.
(5) seawater well cementation of the invention is solid particle with spacetabs type fluid loss agent, is easy to store, is readily transported.
(6) seawater well cementation of the invention with spacetabs type fluid loss agent while cement slurry water loss is ensured, have concurrently it is scattered with
Early strong function, this largely reduces well cementation cost, and fundamentally avoid in well cementing process add it is a variety of
Compatibility issues caused by additive.
Brief description of the drawings
The calcium aluminium profiles houghite and the XRD spectrum of seawater well cementation spacetabs type fluid loss agent prepared in Fig. 1 embodiments 1.
Fig. 2 is the infared spectrum that calcium aluminium profiles houghite and seawater well cementation spacetabs type fluid loss agent are prepared in embodiment 1.
Fig. 3 is the scanning that calcium aluminium profiles houghite (a-c) and seawater well cementation spacetabs type fluid loss agent are prepared in embodiment 1
Electron microscope (d-f).
Fig. 4 is the transmission electron microscope picture that seawater well cementation spacetabs type fluid loss agent is prepared in embodiment 1.
Fig. 5 be prepared in embodiment 1 seawater well cementation with spacetabs type fluid loss agent and comparative example the water under the conditions of seawater mixes slurry
Change isothermal calorimetric curve.
Fig. 6 is cement mortar (d- of the striaght cement (a-c) with adding the seawater well cementation spacetabs type fluid loss agent in embodiment 1
F) the ESEM comparison diagram under the conditions of different curing times.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples, but protection scope of the present invention is not implemented
Example limitation embodiment 1
The seawater well cementation preparation method of spacetabs type fluid loss agent, comprises the following steps：
(1) take monomer 25g to be dissolved in 110mL deionized waters, stirred under normal temperature, with the pH of sodium hydrate regulator solution
=6；The ammonium persulfate for accounting for monomer gross mass 0.6% is added, at 70 DEG C, lower reaction 4h is stirred, is cooled to room temperature, obtains quaternary
Anionic copolymer；The monomer is by 2- acrylamide-2-methyl propane sulfonics 78%, maleic acid 4%, N, N- by quality
DMAA 15%, allyl polyglycol 3% form；
The number-average molecular weight of allyl polyglycol is 600；
(2) take 32g mixed nitrate to be dissolved in 100mL deionized waters, be made into solution A；The mixed nitrate be by
Mol ratio 2：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition；15g sodium mixture is taken to be dissolved in 100mL deionized waters
In, it is made into B solution；The sodium mixture be by mol ratio be 2：1 NaOH and NaNO3Composition；In N2Under protective condition, by A
Solution, B solution are added dropwise in 250ml deionized waters simultaneously respectively, and 80 DEG C are stirred 36 hours, and separation of solid and liquid, solid is dried, and is ground
Mill, obtains calcium aluminium profiles houghite；
(3) 4g quaternary anionic copolymer is dissolved in the deionized water boiled of 10 mass times and obtains C solution；Will
1.5g calcium aluminium profiles houghite, which is scattered in the deionized water boiled of 10 mass times, obtains D dispersion liquids；In N2Protect, C is molten
Liquid and the mixing of D dispersion liquids, under the conditions of rotating speed is 400 revs/min, 95 DEG C of reaction 36h；Separation of solid and liquid, washing, solid vacuum are frozen
It is dry, grinding, obtain seawater well cementation spacetabs type fluid loss agent.
Embodiment 2
The seawater well cementation preparation method of spacetabs type fluid loss agent, comprises the following steps：
(1) take monomer 20g to be dissolved in 110mL deionized waters, stirred under normal temperature, with the pH of sodium hydrate regulator solution
=7；The ammonium persulfate for accounting for monomer gross mass 0.4% is added, at 60 DEG C, lower reaction 6h is stirred, is cooled to room temperature, obtains quaternary
Anionic copolymer；The monomer is by 2- acrylamide-2-methyl propane sulfonics 76%, maleic acid 5%, N, N- by quality
DMAA 16%, allyl polyglycol 3% form；
The number-average molecular weight of allyl polyglycol is 1200；
(2) take 25g mixed nitrate to be dissolved in 100mL deionized waters, be made into solution A；The mixed nitrate be by
Mol ratio 1：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition；10g sodium mixture is taken to be dissolved in 100mL deionized waters
In, it is made into B solution；The sodium mixture be by mol ratio be 1：1 NaOH and NaNO3Composition；In N2Under protective condition, by A
Solution, B solution are added dropwise in 250ml deionized waters simultaneously respectively, and 70 DEG C are stirred 48 hours, and separation of solid and liquid, solid is dried, powder
It is broken, obtain calcium aluminium profiles houghite；
(3) 3g quaternary anionic copolymer is dissolved in the deionized water boiled of 10 mass times and obtains C solution；By 1g
Calcium aluminium profiles houghite be scattered in the deionized water boiled of 10 mass times to obtain D dispersion liquids；In N2Protection, by C solution and
D dispersion liquids mix, under the conditions of rotating speed is 200 revs/min, 90 DEG C of reaction 48h；Separation of solid and liquid, washing, solid vacuum freeze-drying, powder
It is broken, obtain seawater well cementation spacetabs type fluid loss agent.
Embodiment 3
The seawater well cementation preparation method of spacetabs type fluid loss agent, comprises the following steps：
(1) take monomer 30g to be dissolved in 110mL deionized waters, stirred under normal temperature, the pH of solution is adjusted with potassium hydroxide
=4；The azo-bis-isobutyrate hydrochloride for accounting for monomer gross mass 0.8% is added, at 80 DEG C, lower reaction 2h is stirred, is cooled to room
Temperature, obtain quaternary anionic copolymer；The monomer is by 2- acrylamide-2-methyl propane sulfonics 82%, Malaysia by quality
Acid 3%, N,N-DMAA 14%, allyl polyglycol 1% forms；
The number-average molecular weight of allyl polyglycol is 1200；
(2) take 40g mixed nitrate to be dissolved in 100mL deionized waters, be made into solution A；The mixed nitrate be by
Mol ratio 3：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition；20g sodium mixture is taken to be dissolved in 100mL deionized waters
In, it is made into B solution；The sodium mixture be by mol ratio be 2：1 NaOH and NaNO3Composition；In N2Under protective condition, by A
Solution, B solution are added dropwise in 250ml deionized waters simultaneously respectively, and 90 DEG C are stirred 24 hours, and separation of solid and liquid, solid is dried, and is ground
Mill, obtains calcium aluminium profiles houghite；
(3) 6g quaternary anionic copolymer is dissolved in the deionized water boiled of 10 mass times and obtains C solution；By 2g
Calcium aluminium profiles houghite be scattered in the deionized water boiled of 10 mass times to obtain D dispersion liquids；In N2Protection, by C solution and
D dispersion liquids mix, under the conditions of rotating speed is 500 revs/min, 100 DEG C of reaction 24h；Separation of solid and liquid, washing, solid vacuum freeze-drying,
Grinding, obtains seawater well cementation spacetabs type fluid loss agent.
Embodiment 4
The seawater well cementation preparation method of spacetabs type fluid loss agent, comprises the following steps：
(1) take monomer 30g to be dissolved in 110mL deionized waters, stirred under normal temperature, the pH of solution is adjusted with potassium hydroxide
=4；The potassium peroxydisulfate for accounting for monomer gross mass 0.8% is added, at 80 DEG C, lower reaction 2h is stirred, is cooled to room temperature, obtains quaternary
Anionic copolymer；The monomer is by 2- acrylamide-2-methyl propane sulfonics 82%, acrylic acid 3%, N, N- by quality
DMAA 14%, allyl polyglycol 1% form；
The number-average molecular weight of allyl polyglycol is 600；
(2) take 40g mixed nitrate to be dissolved in 100mL deionized waters, be made into solution A；The mixed nitrate be by
Mol ratio 3：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition；20g sodium mixture is taken to be dissolved in 100mL deionized waters
In, it is made into B solution；The sodium mixture be by mol ratio be 2：1 NaOH and NaNO3Composition；In N2Under protective condition, by A
Solution, B solution are added dropwise in 250ml deionized waters simultaneously respectively, and 90 DEG C are stirred 24 hours, and separation of solid and liquid, solid is dried, powder
It is broken, obtain calcium aluminium profiles houghite；
(3) 6g quaternary anionic copolymer is dissolved in the deionized water boiled of 10 mass times and obtains C solution；By 2g
Calcium aluminium profiles houghite be scattered in the deionized water boiled of 10 mass times to obtain D dispersion liquids；In N2Protection, by C solution and
D dispersion liquids mix, under the conditions of rotating speed is 500 revs/min, 100 DEG C of reaction 24h；Separation of solid and liquid, washing, solid vacuum freeze-drying,
Grinding crushes, and obtains seawater well cementation spacetabs type fluid loss agent.
Embodiment 5
The seawater well cementation preparation method of spacetabs type fluid loss agent, comprises the following steps：
(1) take monomer 30g to be dissolved in 110mL deionized waters, stirred under normal temperature, the pH of solution is adjusted with potassium hydroxide
=4；The potassium peroxydisulfate for accounting for monomer gross mass 0.8% is added, at 80 DEG C, lower reaction 2h is stirred, is cooled to room temperature, obtains quaternary
Anionic copolymer；The monomer is by 2- acrylamide-2-methyl propane sulfonics 82%, itaconic acid 3%, propylene by quality
Acid amides 14%, allyl polyglycol 1% form；
The number-average molecular weight of allyl polyglycol is 1200；
(2) take 40g mixed nitrate to be dissolved in 100mL deionized waters, be made into solution A；The mixed nitrate be by
Mol ratio 3：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition；20g sodium mixture is taken to be dissolved in 100mL deionized waters
In, it is made into B solution；The sodium mixture be by mol ratio be 2：1 NaOH and NaNO3Composition；In N2Under protective condition, by A
Solution, B solution are added dropwise in 250ml deionized waters simultaneously respectively, and 90 DEG C are stirred 24 hours, and separation of solid and liquid, solid is dried, and is ground
Mill, obtains calcium aluminium profiles houghite；
(3) 6g quaternary anionic copolymer is dissolved in the deionized water boiled of 10 mass times and obtains C solution；By 2g
Calcium aluminium profiles houghite be scattered in the deionized water boiled of 10 mass times to obtain D dispersion liquids；In N2Protection, by C solution and
D dispersion liquids mix, under the conditions of rotating speed is 500 revs/min, 100 DEG C of reaction 24h；Separation of solid and liquid, washing, solid vacuum freeze-drying,
Grinding, obtains seawater well cementation spacetabs type fluid loss agent.
Comparative example 1
A kind of preparation method of AMPS-NNDMA-MA (ANM) ternary short-side chain anionic fluid loss agent, it includes following
Step：
Successively by 31.2g 2- acrylamide-2-methyl propane sulfonics, 1.2g maleic acids, 6g N,N-DMAAs
It is dissolved in 110mL deionized waters；
Stir at normal temperatures, with the pH to 6 of sodium hydrate regulator solution；Addition accounts for the over cure of monomer gross mass 0.6%
Sour ammonium, at 70 DEG C, stirring reaction 4 hours, room temperature is cooled to, vacuum freeze-drying, obtains short-side chain anionic fluid loss agent
ANM。
Comparative example 2
A kind of preparation method of the long pendant anionic type fluid loss agent of AMPS-NNDMA-MA-APEG (ANMA) quaternary, it is wrapped
Include following steps：
Take monomer 25g to be dissolved in 110mL deionized waters, stirred under normal temperature, with the pH=of sodium hydrate regulator solution
6；The ammonium persulfate for accounting for monomer gross mass 0.6% is added, at 70 DEG C, lower reaction 4h is stirred, is cooled to room temperature, obtain quaternary length
Pendant anionic type fluid loss agent (anionic copolymer ANMA)；The monomer is by 2- acrylamide -2- methyl by quality
Propane sulfonic acid 78%, maleic acid 4%, N,N-DMAA 15%, allyl polyglycol 3% form；
The number-average molecular weight of allyl polyglycol is 600；
The performance evaluation of cement mortar is according to national standard SY/T 5504.2-2013 oil well cement additives evaluation method the 2nd
Part：The method of fluid loss agent carries out related experiment.
The performance of dehydration to embodiment and the fluid loss agent of comparative example, fluidity and compression strength is evaluated, evaluation
As a result such as table 1, shown in table 2 and table 3.
The seawater well cementation of table 1 dehydration test result under the conditions of fresh water or seawater mix slurry with spacetabs type fluid loss agent
Note：Cement-slurry method is：800g G levels praise the magnificent fresh water of the fluid loss agent of oil-well cement+4%+44% or seawater.(/ %
Each mean that body fluid loss agent praises the percentage composition of magnificent oil-well cement in G levels)
The seawater well cementation of table 2 different hydration time fluidity test results under the conditions of seawater mixes slurry with spacetabs type fluid loss agent
Note：Cement-slurry method is：800g G levels praise the magnificent seawater of the fluid loss agent of oil-well cement+4%+44%.(/ % is each meant
Fluid loss agent praises the percentage composition of magnificent oil-well cement in G levels)
The seawater well cementation of table 3 different curing time intensity test knots under the conditions of seawater mixes slurry with spacetabs type fluid loss agent
Fruit
Note：Cement-slurry method is：500g G levels praise the magnificent seawater of the fluid loss agent of oil-well cement+4%+44%.Curing condition is：
The lower 60 DEG C of water-baths of normal pressure, (/ % each means that fluid loss agent praises the percentage composition of magnificent oil-well cement in G levels)
As shown in Table 1, control dehydration of the cement mortar with comparative example under the conditions of fresh water mixes slurry containing fluid loss agent of the present invention
Effect difference is little, illustrates that three kinds of fluid loss agents are applied both to fresh water and mix slurry condition；It is corresponding under the conditions of seawater mixes slurry
For comparative example, the cement mortar control dehydration effect of the fluid loss agent containing embodiment 1-5 is substantially better than comparative example, this
Illustrate the fluid loss agent of the present invention has good control dehydration performance under the conditions of seawater mixes slurry.
As shown in Table 2, the fluidity of different hydration times corresponding to fluid loss agent of the invention and comparative example comparatively,
Slightly decline in aquation early flow degree, but with fluid loss agent of the present invention between calcium aluminium profiles houghite laminate it is cloudy
After ionic copolymer gradually discharges, its fluidity is gradually increasing, and fluidity remains in 120min
More than 200mm, illustrate that lasting dispersive property of the fluid loss agent of the present invention for cement mortar under the conditions of seawater mixes slurry is more preferable.
As shown in Table 3, correspond to for comparative example, the cement mortar containing embodiment 1-5 fluid loss agents is in 60 DEG C of conditions
The development of lower intensity is closer to striaght cement, and development trend is also relatively stable, illustrates that the fluid loss agent of the present invention mixes slurry in seawater
Under the conditions of the cement mortar that can effectively alleviate caused by carboxyl in copolymer cross retardation phenomenon.
In summary seawater well cementation of the present invention with spacetabs type fluid loss agent seawater mix slurry under conditions of control dehydration effect compared with
Comparative example is more outstanding, and the slow-release function having due to it so that can be more within the relatively long period
Effective disperse cement particles, so as to reach the purpose persistently disperseed.And compared with calcium aluminium in fluid loss agent of the present invention for comparative example
The crystal seed effect of type houghite, its promotion for hydrated reaction of cement, is greatly alleviated in copolymer caused by carboxyl
Cement mortar cross retardation phenomenon.And these make fluid loss agent of the present invention both ensure the same of dehydration effect under the conditions of seawater mixes slurry
When, have the advantages of scattered and early strong concurrently.
Fig. 1 is the XRD of the calcium aluminium profiles houghite and seawater well cementation spacetabs type fluid loss agent prepared in embodiment 1
Spectrum.As shown in Figure 1 b, the diffraction pattern of calcium aluminium profiles houghite shows the typical layered structure with high-crystallinity, its diffraction
The standard diffraction card (Fig. 1 a) at peak and the calcium aluminium profiles houghite shown in PDF #54-0849 is highly consistent.By anion
After exchanging intercalation, seawater well cementation is significantly moved with the diffraction maximum of spacetabs type fluid loss agent to low-angle, and crystallinity reduces
(Fig. 1 c).And its corresponding interplanar distance in 1.8nm is far above calcium aluminium profiles houghite (d values are 0.8nm), therefore demonstrate,proves
Bright macromolecular substances are had been inserted between calcium aluminium profiles houghite laminate.
Fig. 2 is the infared spectrum that calcium aluminium profiles houghite and seawater well cementation spacetabs type fluid loss agent are prepared in embodiment 1.
As shown in Figure 2 a, calcium aluminium profiles houghite is in 1385cm-1For the absworption peak of nitrate ion in structure, 790,540 and 430cm-1The octahedral lattice vibration of corresponding A l-O and Ca-O respectively.Seawater well cementation is with the typical absorption peak of spacetabs type fluid loss agent as schemed
Shown in 2b：In about 2900cm-1C h bond stretching vibration in alkyl is detected, in 1050cm-1Ehter bond C-O-C is detected in region,
And in 1200cm-1Place detects S-O keys in sulfonic acid group.The stretching vibration peak related to carboxylic acid appear in 1560 and
1455cm-1Near.Most of all, after quaternary anionic copolymer inserts calcium aluminium profiles houghite interlayer, nitrate anion
Absworption peak almost disappears, and shows the nitrate ion between calcium aluminium profiles class neatly fossil laminate by polyanion quaternary anionic
Copolymer replaces.This infrared data combination XRD result confirms that quaternary anionic copolymer is sent out with calcium aluminium profiles houghite
Raw anion exchange intercalation, so as to successfully prepare seawater well cementation spacetabs type fluid loss agent.
Fig. 3 is the ESEM that calcium aluminium profiles houghite and seawater well cementation spacetabs type fluid loss agent are prepared in embodiment 1
Figure.As shown in Figure 3 a, 3b and 3c as shown in, the electron scanning micrograph of calcium aluminium profiles houghite shows discrete and regular six
Side shape crystal grain.By contrast, seawater well cementation is shown in Fig. 3 d, 3e and 3f pattern with spacetabs type fluid loss agent and not advised
Hexagon platy morphology then, and big hexagonal aggregation is formed in the presence of interlayer anion type polymer.
Fig. 4 is the transmission electron microscope picture that seawater well cementation spacetabs type fluid loss agent is prepared in embodiment 1.As illustrated, seawater
Well cementation spacetabs type fluid loss agent particle has typical layered structure, and concealed wire represents the skeleton of calcium aluminium profiles houghite layer, and bright
Qu Ze represents the interlamellar spacing that anionic polymer occupies.These results indicate that seawater well cementation spacetabs type fluid loss agent is passing through
After going through anion exchange intercalation, its layer structure remains intact, so as to exchange wound with anion in cement mortar for it
Favourable condition is made.
Fig. 5 be prepared in embodiment 1 seawater well cementation with spacetabs type fluid loss agent and comparative example the water under the conditions of seawater mixes slurry
Change isothermal calorimetric curve.From FIG. 5 it is apparent that three kinds of fluid loss agents have different shadows to the hydration of cement
Ring.On the one hand, the comparative example fluid loss agent absorption containing unsaturated carboxyl has delayed hydrated cementitious on hydrolysis product of cement,
Cause the main aquation peak of aquation accelerated period to move right, and reduce total thermal discharge of aquation.On the other hand, embodiment 1
Its crystal structure of the aluminium profiles houghite of offer and single sulfur type aluminum calcium salt in hydrolysis product of cement are very much like, so its
Hydrated cementitious speed and degree are promoted, so that its cement mortar hydration rate and accumulative exotherm be closer to striaght cement,
And obvious retardation phenomenon is not observed.Prove that seawater well cementation spacetabs type fluid loss agent is advantageous to improve early stage really
Hydrated cementitious speed.
Fig. 6 is cement mortar (d- of the striaght cement (a-c) with adding the seawater well cementation spacetabs type fluid loss agent in embodiment 1
F) the ESEM comparison diagram under the conditions of different curing times.As shown in Fig. 6 a and d, seawater well cementation drops dehydration with spacetabs type
The structure of agent cement mortar is more finer and close than striaght cement, and we can see that the sea that addition embodiment 1 provides from comparison diagram
Water well cementation with hydrated cementitious after spacetabs type fluid loss agent formed the crystal such as more entringite and calcium hydroxide (Fig. 6 b, c, e,
F), this data also with strength development before matches, it was demonstrated that seawater well cementation spacetabs type fluid loss agent is advantageous to delay really
Solution cement mortar caused by unsaturated carboxyl in polyanion additive crosses retardation phenomenon.
Claims (10)
1. the preparation method of seawater well cementation spacetabs type fluid loss agent, its feature comprise the following steps：
(1) take monomer 20-30g to be dissolved in 110mL deionized waters, stirred under normal temperature, adjust the pH=4-7 of solution；Add
Monomer gross mass 0.4%-0.8% initiator is accounted for, at 60-80 DEG C, lower reaction 2-6h is stirred, is cooled to room temperature, obtains quaternary
Anionic copolymer；The monomer is by 2- acrylamide-2-methyl propane sulfonic 76%-82%, unsaturated carboxylic acid by quality
3%-5%, acrylic amide material 14%-16%, allyl polyglycol 1%-3% composition；
(2) take 25-40g mixed nitrate to be dissolved in 100mL deionized waters, be made into solution A；The mixed nitrate is by rubbing
You compare 1-3：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition；10-20g sodium mixture is taken to be dissolved in 100mL deionizations
In water, B solution is made into；It by mol ratio is 1-2 that the sodium mixture, which is,：1 NaOH and NaNO3Composition；In N2Under protective condition,
Solution A, B solution are added dropwise in 250ml deionized waters simultaneously respectively, 70-90 DEG C of stirring 24-48 hour, separation of solid and liquid, solid
Dry, grinding or crushing, obtain calcium aluminium profiles houghite；
(3) 3-6g quaternary anionic copolymer is dissolved in the deionized water boiled of 10 mass times and obtains C solution；By 1-2g
Calcium aluminium profiles houghite be scattered in the deionized water boiled of 10 mass times to obtain D dispersion liquids；In N2Protection, by C solution and D
Dispersion liquid mixes, and under the conditions of rotating speed is 200-500 revs/min, reacts 24-48h at 90-100 DEG C；Separation of solid and liquid, washing, solid
Vacuum freeze-drying, grinding or crushing, obtain seawater well cementation spacetabs type fluid loss agent.
2. according to the method for claim 1, it is characterized in that initiator is ammonium persulfate, potassium peroxydisulfate or the NSC 18620 of azo two
Hydrochloride.
3. according to the method for claim 1, it is characterized in that unsaturated carboxylic acid is maleic acid, acrylic acid and itaconic acid.
4. according to the method for claim 1, it is characterized in that acrylic amide material is acrylamide or N, N- dimethyl propylene
Acrylamide.
5. according to the method for claim 1, it is characterized in that the number-average molecular weight of allyl polyglycol is 600-1200.
6. according to the method for claim 1, it is characterized in that step (1) reaction time is 4h.
According to the method for claim 1,7. it is characterized in that the mixed nitrate is by mol ratio 2：1 Ca (N03)2.4H20 and A1 (N03)3.9H20 composition.
8. according to the method for claim 1, it is characterized in that sodium mixture be by mol ratio be 2：1 NaOH and NaNO3Group
Into.
9. spacetabs type fluid loss agent is used in seawater well cementation prepared by the method described in one of claim 1-8.
10. the application of the seawater well cementation spacetabs type fluid loss agent of claim 9.
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