CN105199690A - Oil well cement high temperature resistance suspending agent - Google Patents
Oil well cement high temperature resistance suspending agent Download PDFInfo
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- CN105199690A CN105199690A CN201410285681.0A CN201410285681A CN105199690A CN 105199690 A CN105199690 A CN 105199690A CN 201410285681 A CN201410285681 A CN 201410285681A CN 105199690 A CN105199690 A CN 105199690A
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Abstract
The invention relates to an oil well cement high temperature resistance suspending agent. The oil well cement high temperature resistance suspending agent is prepared from well drilling bentonite and a hydrophobic association water-soluble polymer on the basis that the mass ratio is 5:1. A hydrophobic associated compound is a quadripolymer synthetized by adopting the soap-free emulsion polymerization method. A polymerization monomer comprises, by mass, 35-80 parts of 2-acrylamide-2-methyl propyl sulfonic acid, 10-60 parts of acrylamide, 5-10 parts of N,N-dimethyl acrylamide and 5-20 parts of a monomer containing hydrophobic groups. The high temperature resistance suspending agent can resist the temperature of 170 DEG C, the stability of cement slurry can be effectively achieved, the oil well cement high temperature resistance suspending agent cannot be excessively thickened at low temperature and cannot be excessively diluted at high temperature, and the comprehensive performance is good.
Description
Technical field
The present invention relates to the cement additive that oilfield well completion technology well cementation field is used, is a kind of high temperature resistant suspension agent, is mainly used in improving grout stability, effectively controls grout free liquid.
Background technology
Oil/gas Well will carry out cementing job before recovering the oil, and to reach packing oil, gas, water layer, stops the mutual channelling of ground interlayer fluid-phase, the object of protection productive zone.Cementing job requires that grout will have good over-all properties, to ensure safe construction and good sealing quality.Grout stability is one of grout important performance indexes, and grout stability missionary society causes following harm: compactness extent and the consolidation strength of (1) Behavior of Hardened Cement Paste can constantly weaken from top to bottom, cause detrimentally affect to the sealing quality of cement mantle; (2) in concrete column, form the passage of oil, gas, water breakthrough, affect cementing quality and construction safety, show particularly outstanding in horizontal well and long horizontal traverse well; (3) loose, the strength degradation of upper wellbore cement bond, may cause stratum sealing inefficacy and resident fluid migration, reduce the controllability to reservoir.Therefore, grout stability should attract great attention.
The stability of grout mainly comprises free liquid and sedimentation stability two aspect, the performance that free liquid is few, sedimentation stability is well grout stability.At present, less to the research of grout stability, only free liquid is evaluated before most domestic reinforcing oil well, little to the sedimentation stability evaluation of grout, also effective terms of settlement is lacked after finding serious sedimentation, especially the increasing gradually of high temperature deep well, high temperature sedimentation has become a common problem of cementing the well at present and facing.Much more on-the-spot employing adds the super-fine material such as silicon in a subtle way and, to improve grout stability, but slurry often can be caused too thick and effectively can not suppress the thinning sedimentation caused of high temperature.
Grout suspension agent is used in grout a kind of oil well cement additive stoping particles settling, increase system stability specially.Grout suspension agent be well cementation admixture in develop more late, a kind of material that kind is less.Mainly include organic polymer, biological polymer, water glass and wilkinite, attapulgite, silicon ash etc.Along with the raising that people require cementing quality, the exploitation of suspension agent also comes into one's own gradually.The applicable product amount of current well cementation suspension agent is little; and the limited over-all properties of temperature resistant capability is not good enough, low temperature thickening often can be there is serious, the problem that high temperature too dilutes; limit suspension agent dosage and can adaptive temperature scope, high temperature does not have good suspending power.Some suspension agents also can produce detrimentally affect to performances such as multiviscosisty, intensity, dehydrations, thus affect cementing quality.Therefore, research temperature resistant capability is strong, and the good high temperature resistant suspension agent of over-all properties has great importance.
Summary of the invention
The object of this invention is to provide the high temperature resistant suspension agent of a kind of oil well cement, this suspension agent heatproof can reach 170 DEG C, and over-all properties is good, effectively can solve grout and stablize poor problem, thus ensures construction safety and improve cementing quality.
High temperature resistant suspension agent provided by the invention is the mixture of drilling well wilkinite and a kind of hydrophobic associated water-soluble polymer, and composite optimum proportion is 5:1 (mass ratio).Wherein, hydrophobic associated water-soluble polymer employing is easy to industrialized emulsifier-free emulsion polymerization method and obtains, polymerization single polymerization monomer is 2-acrylamide-2-methylpro panesulfonic acid, acrylamide, N, N-DMAA and one are containing hydrophobic grouping material, and the monomer containing hydrophobic grouping is selected from vinylbenzene, allyl dimethyl base octadecyl ammonium chloride, butyl acrylate.Four kinds of monomer weight part proportionings are: 2-acrylamide-2-methylpro panesulfonic acid 35 ~ 80 parts, acrylamide 10 ~ 60 parts, N, N-DMAA 5 ~ 10 parts, the monomer containing hydrophobic grouping 5 ~ 20 parts.
The concrete preparation method of described high temperature resistant suspension agent is as follows: in beaker, add appropriate distilled water; 2-acrylamide-2-methylpro panesulfonic acid, acrylamide, N is taken according to above-mentioned quality proportioning; N-dimethacrylamide monomers stirring and dissolving in container; then sodium hydrate regulator solution pH=7 is added; pour in the three-necked bottle cleaned up; add again take containing hydrophobic grouping monomer, open and stir and heating unit, and be filled with nitrogen protection.Initiator is added when system temperature reaches 50 DEG C, initiated polymerization, temperature remains on 85 ~ 100 DEG C, isothermal reaction 5h obtains the aqueous solution of thick hydrophobic associated water-soluble polymer, purify by washing with alcohol, then pour in pallet, put into baking oven, at 100 ~ 150 DEG C, carry out drying, finally grinding obtains pure powdery product.Drilling well wilkinite and hydrophobic associated water-soluble polymer pressed powder are mixed by the mass ratio of 5:1 and can obtain high temperature resistant suspension agent product.Initiator used is redox species.
The present invention has following beneficial effect:
(1) composite mode is adopted, the mechanism of suspension agent thickening, thixotroping and formation spatial grid structure has organically been combined in one piece, suspension agent is made all to have good suspending power at low temperatures and high temperatures, significantly can improve the stability of grout, application of temperature, up to 170 DEG C, can meet the needs of growing brill Well Completion Engineering of Oil Reservoirs.
(2) drilling well wilkinite can water-swelling and form thixotropic gel mineral gradually, there is stronger high temperature suspending power, and low temperature thickening is not obvious, the undue thickening of low temperature can be avoided with a small amount of hydrophobic associated water-soluble polymer is composite, ensure carrying out smoothly of construction.
(3) mode of emulsifier-free emulsion polymerization is adopted to synthesize hydrophobic associated water-soluble polymer by introducing hydrophobic monomer, can heat resistance and salt tolerance be there is in hydrophobic association polymer, generation dynamic physical is cross-linked, viscosifying action is obvious, and its viscosity affects less by ionogen, temperature, in certain temperature range, there will not be the thinning phenomenon of serious high temperature, thus keep the high-temperature stability of grout.
(4) a small amount of high temperature resistant suspension agent just can significantly improve grout stability, has no adverse effects to other performances of grout (as thickening time, dehydration, ultimate compression strength etc.).
Accompanying drawing explanation
Figure 117 0 DEG C of concrete column density distribution situation.
Embodiment
Monomer containing hydrophobic grouping is selected from vinylbenzene, allyl dimethyl base octadecyl ammonium chloride or butyl acrylate.Initiator used is Potassium Persulphate and sodium bisulfite redox system.
Embodiment 1:
Take 2-acrylamide-2-methylpro panesulfonic acid 65 parts, acrylamide 25 parts, N, N-DMAA 5 parts is in beaker, stirring and dissolving, then add sodium hydrate regulator solution pH=7, pour in the three-necked bottle cleaned up, then add 5 parts containing hydrophobic grouping monomer, open and stir and heating unit, be filled with nitrogen.0.6 part of initiator is added, initiated polymerization, isothermal reaction 5h stopped reaction when system temperature reaches 50 DEG C.Synthetic product washing with alcohol purifying, drying, grinding are obtained pressed powder, drilling well wilkinite and hydrophobic associated water-soluble polymer pressed powder is mixed by the mass ratio of 5:1 and makes high temperature resistant suspension agent, be labeled as 1# sample.
Embodiment 2:
Take 2-acrylamide-2-methylpro panesulfonic acid 55 parts, acrylamide 30 parts, N, N-DMAA 5 parts of stirring and dissolving in beaker, then sodium hydrate regulator solution pH=7 is added, pour in the three-necked bottle cleaned up, add 10 parts again containing hydrophobic grouping monomer, open and stir and heating unit, be filled with nitrogen.0.6 part of initiator is added, initiated polymerization, isothermal reaction 5h stopped reaction when system temperature reaches 50 DEG C.Synthetic product washing with alcohol purifying, drying, grinding are obtained pressed powder, drilling well wilkinite and hydrophobic associated water-soluble polymer pressed powder is mixed by the mass ratio of 5:1 and makes high temperature resistant suspension agent, be labeled as 2# sample.
Obtained high temperature resistant suspension agent properties of sample is evaluated
According to the test method of regulation in GB/T19139-2012 " oil-well cement test method ", sample is evaluated.Fig. 1 and table 1 for adding the estimation of stability of the grout of suspension agent 1#, 2# sample under high temperature, table 2 be suspension agent 1#, 2# sample to the effect appraise of the rheological property of grout, table 3 is that suspension agent 1#, 2# sample is to the effect appraise of other performances of grout.Evaluate grout basic components (mass ratio) used for G class g cement 100+ silica flour 35+ retardant 2.5+ water retaining 5.0+ water 55.0+ suspension agent sample (dosage is in shown in Table) (cement slurry density 1.87g/cm3).
(1) test does not add suspension agent and adds the grout stability of suspension agent 1#, 2# sample at 170 DEG C, and test result is in table 1 and Fig. 1.
Grout stability test result at table 1170 DEG C
| Suspension agent dosage (accounting for cement quality, %) | Free liquid, % | Concrete column maximum density is poor, g/cm3 |
| 0.0 | 3.5 | 0.40 |
| 1.0 (1# samples) | 0.0 | 0.03 |
| 1.0 (2# samples) | 0.0 | 0.04 |
(note: the concrete column generation significant shrinkage not adding suspension agent sample, top is one deck free liquid)
From above-mentioned experimental result, add 1# (or 2#) the suspension agent sample of 1%, free liquid and the density difference of grout all obviously reduce, grout stability be improved significantly.
(2) test 1#, 2# suspension agent sample under different dosage, the rheological data changing conditions of 20 DEG C and 90 DEG C, test result is as table 2.
Normal temperature and 90 DEG C of rheological data under the different dosage of table 2 suspension agent sample
As shown in Table 2: the grout rheological data adding 1# (or 2#) suspension agent sample, 20 DEG C change not quite with the detected result of 90 DEG C, and rheological data is relatively stable, and compare rheological data increase under normal temperature with the grout not adding suspension agent sample less.This also illustrates, the thickening within reason of 1# (or 2#) suspension agent sample low temperature, and can suppress the thinning phenomenon of high temperature to a certain extent, thus can ensure that grout has good rheological property and sedimentation stability.
(3) test 1#, 2# suspension agent sample other performances of grout under different dosage, probe temperature is 145 DEG C, and test result is as table 3.
Table 3 grout over-all properties table
As shown in Table 3,1# (or 2#) suspension agent sample not only can significantly improve grout stability, and has no adverse effects to performances such as grout multiviscosisty, dehydration and ultimate compression strength.
Experiment proves, high temperature resistant suspension agent of the present invention effectively can solve the stability problem of grout, at 170 DEG C, still there is good suspending power, and low temperature thickening within reason, high temperature dilute not too much, having no adverse effects to other performances of grout, is the good high temperature resistant suspension agent of a kind of over-all properties.
Claims (3)
1. the high temperature resistant suspension agent of oil well cement, is characterized in that: obtained by quality 5:1 is composite by drilling well wilkinite and a kind of hydrophobic associated water-soluble polymer;
Described hydrophobic association polymer is the tetrapolymer adopting the synthesis of emulsifier-free emulsion polymerization method, polymerization single polymerization monomer composition quality proportioning is: 2-acrylamide-2-methylpro panesulfonic acid 35 ~ 80 parts, acrylamide 10 ~ 60 parts, N, N-DMAA 5 ~ 10 parts, the monomer containing hydrophobic grouping 5 ~ 20 parts.
2. the high temperature resistant suspension agent of oil well cement according to claim 1, is characterized in that: described hydrophobic associated water-soluble polymer adopts emulsifier-free emulsion polymerization method to prepare, and initiator used is redox species.
3. the high temperature resistant suspension agent of oil well cement according to claim 1, is characterized in that: the described monomer containing hydrophobic grouping is selected from vinylbenzene, allyl dimethyl base octadecyl ammonium chloride or butyl acrylate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641683A (en) * | 2018-03-30 | 2018-10-12 | 中国石油大学(华东) | A kind of high temperature resistance high salinity high-density water-based drilling fluid and its application |
| CN109456740A (en) * | 2018-09-26 | 2019-03-12 | 西安石油大学 | Modified magnetic nano thickening agent of a kind of hydrophobic associated polymer and preparation method thereof |
| CN109824822A (en) * | 2019-01-28 | 2019-05-31 | 中国石油大学(华东) | Temperature response type high temperature retarder suitable for oil gas well cementing operation and preparation method thereof and cementing slurry |
| WO2020005255A1 (en) * | 2018-06-28 | 2020-01-02 | Halliburton Energy Services, Inc. | Emulsion polymerized cement suspension agent |
| CN112300323A (en) * | 2020-10-15 | 2021-02-02 | 天津中油渤星工程科技有限公司 | Drag-reducing viscosity reducer for oil well cement and preparation method thereof |
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| CN109456740B (en) * | 2018-09-26 | 2021-03-30 | 西安石油大学 | Hydrophobic association polymer modified magnetic nano thickener and preparation method thereof |
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| CN109824822B (en) * | 2019-01-28 | 2021-04-06 | 中国石油大学(华东) | Temperature response type high-temperature retarder suitable for oil-gas well cementation, preparation method thereof and well cementation cement slurry |
| CN112300323A (en) * | 2020-10-15 | 2021-02-02 | 天津中油渤星工程科技有限公司 | Drag-reducing viscosity reducer for oil well cement and preparation method thereof |
| CN112300323B (en) * | 2020-10-15 | 2022-06-03 | 天津中油渤星工程科技有限公司 | Drag-reducing viscosity reducer for oil well cement and preparation method thereof |
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