A kind of geothermal well well cementing mortar architecture and preparation method thereofTechnical field
The present invention relates to cement field, and in particular to a kind of geothermal well well cementing mortar architecture and preparation method thereof.
Background technology
China is the country of geothermal energy resources relative abundance, and geothermal energy resources total amount accounts for the 7.9% of the whole world, and recoverable reserves is suitableIn 4626.5 hundred million tons of standard coals, thermally the presence in the form of high-temperature geothermal of the resource overwhelming majority (is higher than 150 DEG C for western ChinaSteam), geothermal energy resources can not only provide clean energy resource but also be a kind of for works such as extraction bromine, iodine, borax, sylvite, ammonium saltsThe hot brine resource of industry raw material and natural rich water resource.In today that environmental pressure is huge and promotes new energy to develop, underground heat moneySource will be fully utilized.
Geothermal well well cementation is similar with superhigh temperature oil gas well cementing operation, and cement mortar will undergo shaft bottom superhigh temperature during note replaces,Usually above 200 DEG C, Behavior of Hardened Cement Paste is subjected to more than 150 DEG C of high temperature for a long time in the certain annular space length in underground.Geothermal well is cemented the wellWith superhigh temperature well cementation part is slightly different to be, the well cementation of oil/gas well superhigh temperature it is most of for the not long temperature difference of drilling liner cementing interval isolation notGreatly, and the high-temperature geothermal resource of geothermal well is present in underground in the form of high-temperature steam, when well cementation, requires sealing integrality cementSlurry is returned to well head, thus superhigh temperature exists at the same time with the super large temperature difference in geothermal well well cementation.
Foreign vendor is rare in the mortar architecture of the live practical application of geothermal well well cementation at present, and at present there is no 180 DEG CThickening time reaches 200min and returns to well head, and the report of the cement-slurry method of intensity is played in 72h.Also, existing cement mortarSystem is subjected to more than 110 DEG C of high temperature for a long time, it may appear that strength retrogression by a relatively large margin.Research shows that addition accounts for cement ratio before35% or more silica flour of example can prevent such decline, but existing research and live actual production show：Silica flour cannotSuch decline is effective against, even added with 35% and above silica flour (quartz sand) Behavior of Hardened Cement Paste, the hot conditions more than 150 DEG CUnder strength retrogression by a relatively large margin also occurs, occur that annular space is with pressure, reduces a systems such as recovery ratio after cement strength declineRow problem, even results in the well and scraps.
The content of the invention
The technical problems to be solved by the invention are：Mortar architecture of the prior art is not suitable for superhigh temperature and super largeThe problem of simultaneous geothermal well of the temperature difference is cemented the well is, and it is an object of the present invention to provide a kind of geothermal well well cementing mortar architecture, passes through formulaOptimization, be not only only capable of effectively reaching more than 220 DEG C of thickening time 200min, play intensity at the top of cement mortar in 72h, meet underground heatSuperhigh temperature and the simultaneous demand of the super large temperature difference in well well cementation；And the compression strength more than 220 DEG C can also be effectively ensured,Prevent the decline of compression strength.
The present invention is achieved through the following technical solutions：
A kind of geothermal well well cementing mortar architecture, including dry ash, oil-well cement fluid loss agent BFL-12L and high temperature slow settingAgent BRT-22L；Oil-well cement is with the 0%-2% that the addition of drag reducer BFR-31L is dry ash.
Wherein, with weight percentage, oil-well cement is with the 6%-8% that fluid loss agent BFL-12L additions are dry ash；High temperatureRetarder BRT-22L additions are the 5%-9% of dry ash；
Dry ash includes：Oil well G class g cements, the high temperature for accounting for oil well G class g cement quality 50%-100% anti-ageing move back agent BHS-70S, accounts for micro- silicon of oil well G class g cement quality 0%-5%, accounts for the high temperature resistance stabilizer of oil well G class g cement quality 0.6%-1.0%BCS-400S。
Coordinated in the present invention by the optimization of each constituent and proportioning, can meet that 220 DEG C of thickening times are adjustable, be thickenedTime can reach more than 200min, and no extra retarded set, meets construction technology condition, ensures the integrality of pit shaft sealing, meets underground heatSuperhigh temperature and the simultaneous demand of the super large temperature difference in well well cementation.
Meanwhile learnt by detection, the present invention plays intensity in 72h, can reach 35.4MPa at 3 days, delays to 28 days intensitySlowly rise to 37.8MPa and then long-term value preserving is stablized, the compression strength of 98 days reaches 37.2MPa, the compression strength of 98 days and 28Its holding is basically identical.Thus, the compression strength more than 200 DEG C can be effectively ensured in the present invention, prevent the decline of compression strength,Effect is very notable.
Above-mentioned oil-well cement is that our company is on sale with fluid loss agent BFL-12L and oil-well cement with drag reducer BFR-31LProduct, repeats no more in the concrete composition present invention.
Wherein, included with weight percentage, the anti-ageing agent BHS-70S that moves back of the high temperature：
Anti-ageing G grades of high sulfate resisting water of oil well for moving back agent BHS-70S and being suitable for domestic all labels of high temperature in the present inventionMud, the high temperature is anti-ageing to move back agent BHS-70S and shows that chemical inertness does not influence the live mixture of cement mortar and note replaces at normal temperatures.CarryThe high cement slurry effect that anti-compression strength fails under the high temperature conditions, and effect is very notable.
The high temperature retarder BRT-22L includes：
Preferably, the monomer concentration of the high temperature retarder BRT-22L is 20wt%-35wt%.
The raw material of the high temperature resistance stabilizer BCS-400S includes：
Polymer retarder nearly all reaches deferred action using single carboxylate radical monomer in the prior art, and temperature exceedes180 DEG C of high temperature retarder failure or dosage increased dramatically, retarder dosage and thickening time not in a linear relationship thickening timeIt is non-adjustable.Reached in the prior art by the way of compounding polyol, organic phosphoric acid (salt) and extend the thickening time, resistThe purpose of high temperature, but such compounding frequently result in the drop dehydration effect for influencing fluid loss agent, thickening curve bulge, not salt resistance,The use under hot conditions again is limited at the top of the big temperature difference situations such as extra retarded set.
Present invention optimizes the compounded formula of high temperature retarder BRT-22L, can apply under the high temperature conditions, especiallyUnder hot conditions more than more than 180 DEG C, it can also make retarder dosage and thickening time in a linear relationship, easy to the thickening timeAdjustment, convenient operation.And the optimization that the present invention is compounded by high temperature retarder BRT-22L, makes the side base of material of the present inventionIncrease, and then the benzene sulfonic acid group that can effectively make to generate under high temperature is reduced, and reduces hydrolysis, avoids influencing the drop dehydration of fluid loss agentEffect；Meanwhile thickening curve bulge can also effectively be avoided by the optimization of formula, reach salt resistance, will not go out at the top of the big temperature differenceExisting extra retarded set and other effects.
A kind of preparation method of geothermal well well cementing mortar architecture, including：
Step 1: being respectively configured, high temperature is anti-ageing to move back agent BHS-70S, high temperature retarder BRT-22L, high temperature resistance stabilizer BCS-400S；
Step 2: by high temperature it is anti-ageing move back agent BHS-70S, high temperature retarder BRT-22L, high temperature resistance stabilizer BCS-400S,Micro- silicon, oil-well cement drag reducer BFR-31L, oil-well cement are with BFL-12L, G grades of oil-well cements of fluid loss agent according to GB/T19139-2012《Oil-well cement experimental method》Prepare cement mortar
Further, the preparation method of the high temperature resistance stabilizer BCS-400S is as follows：
By vinyl pyrrolidone, acrylamide, N, N- dimethacrylamide, acryloyl morpholine and water are after mixingIt is configured to solution, adjusts pH value of solution to after 6.5~7.5, be added in reaction vessel, and N is passed through in reaction vessel2Protection,The initiator for adding solution solid content 2.0%-3.0% at 40~50 DEG C is reacted；After reacting 3~5h, obtained by dryingObtain finished product.
Further, the high temperature it is anti-ageing move back agent BHS-70S preparation method it is as follows：
Photovoltaic silicon, aerosil, dead burned magnesia and mineral fibres are uniformly mixed.
Further, the preparation method of the high temperature retarder BRT-22L is as follows：
By AMPS, acrylamide, itaconic acid, maleic anhydride, acryloyl morpholine and water be uniformly mixed and adjust pH value of solution toAfter 6.5~7.0, it is added in reaction vessel, and N is passed through in reaction vessel2Protection, 40~55 DEG C of whens, add monomer massThe initiator of 2.0%-3.0% carries out radical polymerization；Start timing, 1~1.5h of timing when being reacted to and reaching maximum temperature pointAfter obtain finished product.
Preferably, pH is adjusted by NaOH in the preparation method of the high temperature retarder BRT-22L, pH is adjusted to 6.5.InstituteThe temperature stated when initiator adds is 50 DEG C, and the time of timing is 1h.
Compared with prior art, the present invention have the following advantages and advantages：
1st, the present invention is not only only capable of effectively making 220 DEG C of thickening times reach more than 200min, plays intensity in 72h, contentedlySuperhigh temperature and the simultaneous demand of the super large temperature difference in hot well well cementation；And the intensity more than 200 DEG C can also be effectively ensured, dropLow intensive decline；
2nd, technique of the invention is simple, relative inexpensiveness, and environmental-friendly, effect is very notable.
Brief description of the drawings
Attached drawing described herein is used for providing further understanding the embodiment of the present invention, forms one of the applicationPoint, do not form the restriction to the embodiment of the present invention.In the accompanying drawings：
Fig. 1 is Behavior of Hardened Cement Paste electromicroscopic photograph made of embodiment 1.
Fig. 2 is Behavior of Hardened Cement Paste electromicroscopic photograph made of embodiment 9.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment, the present invention is madeFurther to describe in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to thisThe restriction of invention.
Embodiment 1
A kind of geothermal well well cementing mortar architecture, including dry ash, fluid loss agent BFL-12L, drag reducer BFR-31L and high temperatureRetarder BRT-22L；Wherein, high temperature is anti-ageing moves back BCS-400S and G grades of agent BHS-70S, micro- silicon, high-temperature stabilizer oil-well cements oneRise and form dry ash.
High temperature retarder BRT-22L includes AMPS (2- acrylamido -2- methyl propane sulfonic acids), acrylamide, clothing healthAcid, maleic anhydride, acryloyl morpholine and water.
High-temperature stabilizer BCS-400S includes vinyl pyrrolidone, acrylamide, N, N- dimethacrylamide, propyleneMorpholide and water.
The preparation method of the geothermal well well cementing mortar architecture is as follows in the present embodiment：
Step 1: configuring, high temperature is anti-ageing to move back agent BHS-70S：By photovoltaic silicon, aerosil, dead burned magnesia and mineralFiber, which is uniformly mixed, obtains BHS-70S.
Configure high temperature retarder BRT-22L：By AMPS, acrylamide, itaconic acid, maleic anhydride, acryloyl morpholine and waterAfter being uniformly mixed and adjusting pH to 6 by NaOH, it is added in reaction vessel, and N is passed through in reaction vessel2Protection, 50 DEG CWhen add the ammonium persulfate of monomer mass 2.0%-3.0% and carry out radical polymerization；Start when being reacted to and reaching maximum temperature pointTiming, high temperature retarder BRT-22L is obtained after timing 1h.
Configure high-temperature stabilizer BCS-400S：By vinyl pyrrolidone, acrylamide, N, N- dimethacrylamide,Acryloyl morpholine and water are configured to solution after mixing, adjust pH value of solution to after 7, are added in reaction vessel, and reactingN is passed through in container2Protection, the ammonium persulfate that solution solid content 2.0%-3.0% is added at 40~50 DEG C are reacted；ReactionAfter 3~5h, monomer finished product is obtained by dry, high-temperature stabilizer BCS- is made in micro- silicon that its weight 15% is added in monomer finished product400S.The raw material of monomer finished product includes vinyl pyrrolidone 6%, acrylamide 2%, N, N- dimethacrylamide 5%, thirdDimethomorph 15%, remaining is water.
Step 2: by BHS-70S, high temperature retarder BRT-22L, micro- silicon, high-temperature stabilizer BCS-400S, drag reducer BFR-BFL-12L, G grades of 31L, fluid loss agent oil-well cements are uniformly mixed.Behavior of Hardened Cement Paste electromicroscopic photograph such as Fig. 1 made of the present embodimentIt is shown.
The specific proportioning of each material is as follows in the present embodiment：
By G grades of oil-well cements, the high temperature for accounting for G grades of oil-well cement quality 50% anti-ageing move back agent BHS-70S, accounts for G grades of oil dry ashMicro- silicon of well cement quality 0%, the high-temperature stabilizer BCS-400S compositions for accounting for G grades of oil-well cement quality 0.8%, and in dry ashAdd the fluid loss agent BFL-12L, 1.0% drag reducer BFR-31L, 7.0% high temperature retarder BRT-22L of its weight 6%.
The anti-ageing agent BHS-70S that moves back of high temperature is aoxidized by 57% photovoltaic silicon, 22% aerosil, 20% reheatingMagnesium, 1% mineral fibres composition.
2- acrylamido -2- methyl propane sulfonic acid, 3% acryloyl of the raw material of high temperature retarder BRT-22L by 15%Amine, 3% itaconic acid, 3% maleic anhydride, 2% acryloyl morpholine and 74% water composition.
Embodiment 2
The difference of the present embodiment and embodiment 1 is only in the present embodiment high temperature is anti-ageing to move back agent BHS-70S, micro- silicon, GLevel oil-well cement, oil-well cement fluid loss agent BFL-12L, oil-well cement drag reducer BFR-31L and high temperature retarder BRT-The proportioning of 22L is different, and specific setting is as follows：
Dry ash anti-ageing moves back agent BHS-70S, 5% micro- silicon, 20% G level oil-well cements by 75% high temperature in the present embodimentForm, and the oil-well cement fluid loss agent BFL-12L of its weight 7%, 0% oil-well cement drag reducer are added in dry ashBFR-31L, 5% high temperature retarder BRT-22L.
Embodiment 3
The difference of the present embodiment and embodiment 1 is only in the present embodiment high temperature is anti-ageing to move back agent BHS-70S, micro- silicon, GLevel oil-well cement, oil-well cement fluid loss agent BFL-12L, oil-well cement drag reducer BFR-31L and high temperature retarder BRT-The proportioning of 22L is different, and specific setting is as follows：
Dry ash anti-ageing moves back agent BHS-70S, 2% micro- silicon, 8% G level oil-well cements by 90% high temperature in the present embodimentForm, and the oil-well cement fluid loss agent BFL-12L of its weight 8%, 2% oil-well cement drag reducer are added in dry ashBFR-31L, 7% high temperature retarder BRT-22L.
Embodiment 4
The difference of the present embodiment and embodiment 1 is only in the present embodiment high temperature is anti-ageing to move back agent BHS-70S, micro- silicon, GLevel oil-well cement, oil-well cement fluid loss agent BFL-12L, oil-well cement drag reducer BFR-31L and high temperature retarder BRT-The proportioning of 22L is different, and specific setting is as follows：
Dry ash anti-ageing moves back agent BHS-70S, 0% micro- silicon, 0% G level oil-well cements by 100% high temperature in the present embodimentForm, and the oil-well cement fluid loss agent BFL-12L of its weight 8%, 2% oil-well cement drag reducer are added in dry ashBFR-31L, 9% high temperature retarder BRT-22L.
1-4 of the embodiment of the present invention plays intensity in 72h, can reach 35.4MPa at 3 days, is slowly risen to 28 days intensity37.8MPa and then long-term value preserving are stablized, and the compression strength of 98 days reaches 37.2MPa, the compression strength of 98 days and 28 days holding basesThis is consistent.Thus, the compression strength more than 200 DEG C can be effectively ensured in the present invention, prevent the decline of compression strength, effect is verySignificantly.
Embodiment 5
Difference lies in the proportioning of the present embodiment high temperature retarder BRT-22L is different, originally with embodiment 1 for the present embodimentThe specific proportioning of embodiment high temperature retarder BRT-22L is as follows：
High temperature retarder BRT-22L is by 19% 2- acrylamido -2- methyl propane sulfonic acids, 2% acrylamide, 2%Itaconic acid, 2% maleic anhydride, 0% acryloyl morpholine and 75% water composition.
Embodiment 6
Difference lies in the proportioning of the present embodiment high temperature retarder BRT-22L is different, originally with embodiment 1 for the present embodimentThe specific proportioning of embodiment high temperature retarder BRT-22L is as follows：
High temperature retarder BRT-22L is by 12% 2- acrylamido -2- methyl propane sulfonic acids, 5% acrylamide, 5%Itaconic acid, 5% maleic anhydride, 4% acryloyl morpholine and 69% water composition.
Embodiment 7
The present embodiment and embodiment 1 difference lies in, the anti-ageing proportioning for moving back agent BHS-70S of the present embodiment high temperature is different,The present embodiment high temperature is anti-ageing move back agent BHS-70S specific proportioning it is as follows：
The anti-ageing agent BHS-70S that moves back of high temperature is aoxidized by 57% photovoltaic silicon, 15% aerosil, 27% reheatingMagnesium, 1% mineral fibres composition.
Embodiment 8
The present embodiment and embodiment 1 difference lies in, the anti-ageing proportioning for moving back agent BHS-70S of the present embodiment high temperature is different,The present embodiment high temperature is anti-ageing move back agent BHS-70S specific proportioning it is as follows：
The anti-ageing agent BHS-70S that moves back of high temperature is aoxidized by 57% photovoltaic silicon, 27% aerosil, 15% reheatingMagnesium, 1% mineral fibres composition.
Embodiment 9
The present embodiment is the comparative example of embodiment 1, and the composition of dry ash is different in the present embodiment, dry ash in the present embodimentSpecific setting is as follows：
Dry ash includes G grades of high sulfate resisting cement of oil well, accounts for the mineral fibres of G grades of high sulfate resisting cement qualities 1%+account forThe silica flour of G grades of high sulfate resisting cement qualities 49%.Behavior of Hardened Cement Paste electromicroscopic photograph is as shown in Figure 2 made of the present embodiment.
The testing result of embodiment 1-4 and embodiment 9 is as shown in table 1.
Table 1
Pass through the experimental result of above-mentioned table 1：The compression strength more than 200 DEG C can be effectively ensured in the present invention, reduceBehavior of Hardened Cement Paste permeability, reaches the effect for reducing strength retrogression.
Embodiment 10
The present embodiment is the comparative example of embodiment 1, with differing only in for embodiment 1, is used in the present embodimentThe species of high temperature retarder is different.For existing finished product, which is the high temperature retarder used in the present embodimentHigh temperature-resistance oil well cement retarder disclosed in CN201610389412.8, its specific proportioning and manufacturing process are as follows：
Using mass ratio as 16：3：1 ratio weighs sodium p styrene sulfonate (SSS), itaconic acid (IA), N- vinyl in oneselfAcid amides (NVCL), is adjusted pH value to 5 with deionized water dissolving, and by sodium hydroxide solution that concentration is 5mol/L, with12% solid content controls total liquor capacity for standard.
By water-bath temperature adjustment to 60 DEG C, reaction unit is installed, the reaction unit includes three-neck flask, polytetrafluoroThe critical pieces such as ethene rabble, separatory funnel.The mixed solution of sodium styrene sulfonate (SSS) and itaconic acid (IA) is moved into threeIn neck flask, Teflon stir bar keeps the rotating speed of (2000 ± 200 revs/min), and nitrogen deoxygenation is led into container, treats temperatureDesign temperature is risen to, N- caprolactams (NVCL) are added into three-neck flask respectively using separatory funnel and to account for monomer totalThe initiator potassium persulfate of quality 1.0%.
After being added dropwise, maintain rotating speed constant, after reacting 4h at a set temperature, after micro- viscous solution is cooled to room temperatureWith acetone purification 2~3 times, drying, it is ground into powder, up to SSS/IA/NVCL copolymers.
The detection of performance, testing result such as table 2 and table 3 are carried out to above-described embodiment 1 and embodiment 7-8 and embodiment 10It is shown.
Table 2
Table 3
Pass through above-mentioned table 2 and table 3 and experimental result：The present invention can be realized effectively under hot environment, especially superCross under more than 180 DEG C of hot conditions, can also make retarder dosage and thickening time in a linear relationship, easy to the tune of thickening timeWhole, convenient operation, thickening curve bulge can also be effectively avoided by the optimization of formula, reach salt resistance, will not at the top of the big temperature differenceThere is extra retarded set and other effects.
Pass through above-mentioned table 1- tables 3 and figure and experimental result：Cementing slurry of the present invention can be in 220 DEG C of * 110MPa*Under the conditions of 70min, the thickening time, 200min-400min was adjustable, returns to well head cement mortar 72h intensity and starts to develop, meets underground heatSuperhigh temperature and the simultaneous demand of the super large temperature difference in well well cementation；And the Behavior of Hardened Cement Paste more than 200 DEG C can also be effectively ensured to resistCompressive Strength, prevents Behavior of Hardened Cement Paste compression strength from failing.
Above-described embodiment, has carried out the purpose of the present invention, technical solution and beneficial effect furtherDescribe in detail, it should be understood that the foregoing is merely the embodiment of the present invention, be not intended to limit the present inventionProtection domain, within the spirit and principles of the invention, any modification, equivalent substitution, improvement and etc. done, should all includeWithin protection scope of the present invention.