CN102010702A - Oil-well cement additive against carbon dioxide corrosion as well as preparation method and application thereof - Google Patents
Oil-well cement additive against carbon dioxide corrosion as well as preparation method and application thereof Download PDFInfo
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- CN102010702A CN102010702A CN2009101701421A CN200910170142A CN102010702A CN 102010702 A CN102010702 A CN 102010702A CN 2009101701421 A CN2009101701421 A CN 2009101701421A CN 200910170142 A CN200910170142 A CN 200910170142A CN 102010702 A CN102010702 A CN 102010702A
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Abstract
The invention provides an oil-well cement additive against carbon dioxide corrosion as well as a preparation method and application thereof, relating to the field of well cementation of oil-well cement. The oil-well cement additive mainly comprises the following raw materials in percentage by weight of: 20-65%wt of volcanic gray minerals, 2-25%wt of silica fume, 5-25%wt of aluminum salt mineral, 5-35%wt of organic paraffin material, 1-10%wt of methyl silanol sodium, and 3-25%wt of slag. When 15-60 parts of the oil-well cement additive is added into 100 parts of cement, the compactness of cement columns can be strengthened, with low gas permeability and strong resistance against carbon dioxide corrosion. The oil-well cement additive is suitable for different temperatures, and has wider application.
Description
Technical field:
The present invention relates to a kind of oil well cement additive, say further, relate to a kind of oil well cement additive that prevents carbon dioxide corrosion, and its production and application.
Background technology:
Carbonic acid gas is present in the stratum as the component of associated gas in the oil and natural gas production or local water.Carbonic acid gas can be to the oil well cement annulated column under wet environment, and promptly cement stone produces corrosion.As everyone knows, the oil well cement annulated column mainly plays packing oil, gas, water, supports sleeve pipe and protective casing, prolongs the effect in oil gas well life-span.Guide's corrosion of cement annulated column can cause and accelerate the telescopic corrosion and destroy.And may bring out other down-hole accident, shorten the production life-span of oil gas well.
At present domestic to CO
2Though the problem of erode downhole tubing has caused the attention in each oil field, and carried out protection against corrosion research.But oil gas well first protection barrier-oil well cement ring is suffered CO
2Corrosive research is also less, to the anti-CO of cement mantle
2The exploitation of corrosion admixture yet there are no relevant report.Only be the corresponding safeguard procedures of taking at indivedual oil fields, for example: the anti-CO that is applicable to Daqing oil field has studied at the particular case of grand celebration in Daqing Petroleum Administration and Daqing Petroleum Institute
2The corrosive water mud system.Dagang Oilfield adopts Sweet natural gas CO
2Improve the recovery ratio of oil gas, its technical cue is applied filtrate reducer for cement slurry exactly, improves cementing quality, reduces CO
2Drive, CO
2To the corrosion of cement mantle, reduce the potentially dangerous of cement mantle and formation cementation.But above each individual system specific aim in application is very strong, owing to the specific geologic condition in each oil field and the difference of working condition such as temperature, pressure etc. exist than big difference, thereby is difficult to generally promote.
In sum, develop a kind of applied widelyly, can effectively prevent the novel oil well cement additive of carbon dioxide corrosion from becoming the technical problem that needs to be resolved hurrily at present.
Summary of the invention:
Be to solve problems of the prior art, a kind of oil well cement additive that prevents carbon dioxide corrosion provided by the present invention, the described CO that prevents of adding in well cementing mortar architecture
2Can effectively control and prevent and treat the downhole corrosion phenomenon behind the corrosive admixture.
One of purpose of the present invention has provided a kind of oil well cement additive that prevents carbon dioxide corrosion.
Described oil well cement additive comprises following component by weight percentage:
1. volcano grey matter mineral 20～65%wt
2. SILICA FUME 2～25%wt
3. aluminium salt mineral 5～25%wt
4. paraffin class organic materials 5～35%wt
5. methyl silicon sodium alcoholate 1～10%wt
6. slag 3～25%wt.
The above volcano grey matter mineral is the industrial residues that have silica and aluminum-oxygen tetrahedron through incinerating.Its preferred content is 25～60%wt.Volcano grey matter mineral can be through commercially available and get.
The above aluminium salt mineral is γ and alpha-type aluminum oxide mixture, and its median size is 50～300nm.Its preferred content is 5～20%wt.Aluminium salt mineral can be through commercially available and get.
The above paraffin class organic materials is that nonionic surface active agent and the emulsification of paraffin class material get, and its median size is 50～500nm.Its preferred content is 10～30%wt.Described paraffin class organic materials originates from oilfield additive research and development centre of petroleum engineering research institute of China Petrochemical Industry Dezhou petroleum drilling institute, and by its sale.Its commodity are called " DC201 impregnating material ".
The above SILICA FUME is a fine silica powder, and its median size is 1～10 μ m.Its preferred content is 5～20%wt.SILICA FUME can be passed through commercially available and be got.
The preferred content of the above methyl silicon sodium alcoholate is 3～8%wt.It can pass through commercially available and get.
The above slag, its preferred content are 5～20%wt.Can be through commercially available and get.
The oil well cement additive that prevents carbon dioxide corrosion provided by the present invention can also add cementing cement system auxiliary agent commonly used in other prior aries, and as agent for anti gassing-out etc., consumption can be according to routine.
The oil well cement additive that prevents carbon dioxide corrosion provided by the present invention, be based on inorganic materials, can form the continuous three-dimensional network framework mineral that closed chain constitutes under certain conditions, combine with organic substance, in the carbonic acid environment, can make cement stone form tight zone, thereby reduce the rate of permeation of cement stone, prevent CO effectively
2Erosion, improve the resistance to corrosion of cement stone.
Two of purpose of the present invention provides the described preparation method who prevents the oil well cement additive of carbon dioxide corrosion, and it may further comprise the steps:
(1) takes by weighing volcano grey matter mineral, SILICA FUME, aluminium salt mineral and slag by described content, grind to puddle to mixture and reach 200 order fineness at least.
(2) mixture that step (1) is made and other comprise that the component of described emulsified olefin, methyl silicon sodium alcoholate puts into mixing machine by described content and mix, and after mixing, make the described oil well cement additive that prevents carbon dioxide corrosion.Prepared oil well cement additive is generally the grey powder-product.
The grinding that relates among the preparation method, mixing equipment are industry common equipment, as: dry ball, double worm mixer etc.In step (2),, can in mixing machine, puddle at least 2 hours for making mixing more even.
Three of purpose of the present invention provides the described application of oil well cement additive in the oil well cement well cementation that prevents carbon dioxide corrosion.
The oil well cement additive of carbon dioxide corrosion that prevents of the present invention is added in the mortar architecture of well cementation usefulness, and it can improve the corrosion resistance of cement annulated column.The anti-CO of cement annulated column
2Corrosive nature relevant with the dosage of admixture.Generally speaking can be according to on-the-spot CO
2The content dosage of regulating this admixture satisfy the demand of different scene well cementation conditions.Be 100 parts by weight in well cementation with cement content in the grout generally, with 15～60 parts, preferred 15～45 parts of oil well cement additives of carbon dioxide corrosion that prevent of the present invention add cementing slurry, mix to get final product.
The above cementing slurry is some well cementation mortar architectures of using always in the prior art.Generally speaking can include following component: cement, 100 parts by weight; Silica flour, 10-35 part; Water retaining, 3-6 part; Agent for anti gassing-out, 5-18 part; Dispersion agent and retardant, 1-5 part.Wherein said well cementation be the cement of usefulness of cementing the well usually with the cement in the mortar architecture, can be commercially available and get.Described silica flour is a SiO 2 powder, and its fineness of powder can be crossed 160 mesh sieves, can be commercially available and get; Described water retaining, agent for anti gassing-out, dispersion agent and retardant are well cementation with the usual auxiliaries of cement system, all can be commercially available and get.
Oil well cement additive of the present invention add behind the cementing cement system can refinforced cement stone (cement annulated column) compactness, make cement stone have good carbon dioxide corrosion-resistant ability:
(1) cement stone 24h ultimate compression strength 〉=14MPa;
(2) CO
2Corrosive water mudstone 60 days, ultimate compression strength rate of loss are 0;
(3) CO
260 days gas permeability of corrosive water mudstone does not only increase and reduces on the contrary;
(4) cement stone temperature resistance can reach 150 ℃;
(5) adding prevents CO
2Well cementing mortar architecture rheological property behind the corrosive oil well cement additive meets the cementing operation standard, reaches engine request.
Embodiment:
Below in conjunction with embodiment, further specify the present invention.
The corrosion test method of the oil well cement additive of carbon dioxide corrosion that prevents of the present invention comprises following steps:
(1) pours in the die trial by API standard 10 preparation grouts, be positioned in the high temperature and pressure protective cauldron maintenance 24 hours, take out the demoulding;
(2) cement briquette that will prepare and number (being cement stone) and water are put into corrosion maintenance still, sealing;
(3) feed CO
2And be warming up to test temperature, observe CO at any time
2Pressure, temperature variation are also in time adjusted, and test period can be adjusted as requested, is generally 21 days;
(4) experiment finishes, and the corrosive nature of carrying out sample detects.
Corrosive nature content measurement in the above-mentioned steps (4) comprises: gas permeability, ultimate compression strength change and corrode mineral composition, microscopic pattern, the CO of back cement briquette
2Invasion depth etc.In order to say something general CO
2The corrosion sample wants and the non-corrosive sample under the uniform temp pressure condition compares.
The ultimate compression strength velocity of variation: cement stone corrosion back ultimate compression strength subtracts uncorroded ultimate compression strength difference and does not corrode the ratio of ultimate compression strength, represents with percentage ratio.
The gas-permeable velocity of variation: gas permeability subtracts the difference of the preceding gas permeability of corrosion and the ratio of rotten preceding gas permeability after the corrosion of cement stone, represents with percentage ratio.
1. grey matter mineral in volcano are for having the industrial residue of silica and aluminum-oxygen tetrahedron through incinerating; Aluminium salt mineral are γ and alpha-type aluminum oxide complex body; The paraffin class organic materials is the emulsified material of nonionic surface active agent and paraffin class material.
2. testing used volcano grey matter mineral, paraffin class organic materials (DC201 impregnating material), fluid loss agent DZJ-Y (2 one acrylamidos, one 2 monomethyl propanesulfonic acid and acrylamide polymers), dispersion agent DZS (sulfonated acetone formaldehyde condensation products) retardant DZH (phosphoric acid salt and tartaric compound), agent for anti gassing-out DC200 materials such as (divinyl and cinnamic polymkeric substance) purchases in oilfield additive research and development centre of petroleum engineering research institute of China Petrochemical Industry Dezhou petroleum drilling institute.The place of production of aluminium salt mineral is: the Beijing Jiayi Hengyuan Technology Development Co., Ltd.Other components such as SILICA FUME, silica flour, slag and methyl silicon sodium alcoholate all get by commercially available.
One, prevents the oil well cement additive preparation example of carbon dioxide corrosion
Embodiment 1:
Get 60%wt volcano grey matter mineral, add SILICA FUME 5%wt, slag 5%wt, aluminium salt mineral 15%wt drops in the dry ball, in dry ball levigate and puddle evenly reach 200 order fineness after, put into the duplex mixer again, add 10%wt paraffin class organic materials and methyl silicon sodium alcoholate 5%wt and puddle, puddled repeatedly 2 hours, make gray powder powder admixture 1# product after treating evenly.
Embodiment 2:
Get 40%wt volcano grey matter mineral, add SILICA FUME 15%wt, slag 5%wt, aluminium salt mineral 20%wt drops in the dry ball, in dry ball levigate and puddle evenly reach 200 order fineness after, put into the duplex mixer again, add 17%wt paraffin class organic materials and methyl silicon sodium alcoholate 3%wt and puddle, puddled repeatedly 2 hours, make gray powder powder admixture 2# product after treating evenly.
Embodiment 3:
Get 30%wt volcano grey matter mineral, add SILICA FUME 10%wt, slag 15%wt, aluminium salt mineral 12%wt drops in the dry ball, in dry ball levigate and puddle evenly reach 200 order fineness after, put into the duplex mixer again, add 30%wt paraffin class organic materials and methyl silicon sodium alcoholate 3%wt and puddle, puddled repeatedly 2 hours, make gray powder powder admixture 3# product after treating evenly.
Two, prevent the oil well cement additive application examples of carbon dioxide corrosion
Comparative example 1:
No. 1 system of cementing slurry: good magnificent G cement (magnificent cement mill is praised in Sichuan) 100 parts by weight, silica flour (commercially available) 35 parts by weight, liquid-solid ratio is 0.46.No. 1 system is carried out above-mentioned corrosion test, and related cement briquette is a comparative sample 1.
Comparative example 2:
No. 2 systems of cementing slurry: good magnificent G cement (the same) 100 weight parts, 35 parts of silica flours (the same), 5 parts of fluid loss agent DZJ-Y, 12 parts of agent for anti gassing-out DC200,2 parts of dispersion agent DZS and 1.5 parts of retardant DZH, liquid-solid ratio is 0.46.No. 2 systems are carried out above-mentioned corrosion test, and related cement briquette is a comparative sample 2.
Embodiment 5:
On the basis of No. 2 systems of above-mentioned cementing slurry, add the embodiment 1 prepared carbon dioxide corrosion oil well cement additive 1# product that prevents, mix No. 3 systems of cementing slurry that obtain.Wherein the consumption of 1# product is 100 parts with cement weight in the cementing slurry and counts 35 parts.No. 3 systems are carried out above-mentioned corrosion test, and related cement briquette is a sample 1.
Embodiment 6:
On the basis of No. 2 systems of above-mentioned cementing slurry, add the embodiment 2 prepared carbon dioxide corrosion oil well cement additive 2# products that prevent, obtain No. 4 systems of cementing slurry after mixing.Wherein the consumption of 2# product is 100 parts with cement weight in the cementing slurry and counts 35 parts.No. 4 systems are carried out above-mentioned corrosion test, and related cement briquette is a sample 2.
Embodiment 7:
On the basis of No. 2 systems of above-mentioned cementing slurry, add the embodiment 3 prepared carbon dioxide corrosion oil well cement additive 3# products that prevent, obtain No. 5 systems of cementing slurry after mixing.Wherein the consumption of 3# product is 100 parts with cement weight in the cementing slurry and counts 35 parts.To carry out above-mentioned corrosion test after No. 5 systems, related cement briquette is a sample 3.
Embodiment 8:
On the basis of No. 2 systems of above-mentioned cementing slurry, add the embodiment 2 prepared carbon dioxide corrosion oil well cement additive 2# products that prevent, obtain No. 6 systems of cementing slurry after mixing.Wherein the consumption of 2# product is 100 parts with cement weight in the cementing slurry and counts 15 parts.No. 6 systems are carried out above-mentioned corrosion test, and related cement briquette is a sample 4.
Embodiment 9:
On the basis of No. 2 systems of above-mentioned cementing slurry, add the embodiment 2 prepared carbon dioxide corrosion oil well cement additive 2# products that prevent, obtain No. 7 systems of cementing slurry after mixing.Wherein the consumption of 2# product is 100 parts with cement weight in the cementing slurry and counts 25 parts.No. 7 systems are carried out above-mentioned corrosion test, and related cement briquette is a sample 5.
Embodiment 10:
On the basis of No. 2 systems of above-mentioned cementing slurry, add the embodiment 2 prepared carbon dioxide corrosion oil well cement additive 2# products that prevent, obtain No. 8 systems of cementing slurry after mixing.Wherein the consumption of 2# product is 100 parts with cement weight in the cementing slurry and counts 30 parts.No. 8 systems are carried out above-mentioned corrosion test, and related cement briquette is a sample 6.
1～No. 5 system is tested, and whole test is undertaken by the API standard, and cement briquette corrosive major project performance is judged the corrosion condition of cement briquette with cement briquette ultimate compression strength and gas changes in permeability degree.
Experiment condition: 130 ℃ of test temperatures; CO
2Dividing potential drop is 5.0MPa; Test period is 21 days, and comparing result sees Table 1.
Table 1
Clean as seen from Table 1 slurry and do not add the well cementing mortar architecture CO that the present invention prevents the oil well cement additive of carbon dioxide corrosion
2Seriously corroded, the cement briquette intensity after the corrosion reduces bigger, and gas permeability also increases.The different oil well cement additive of component concentration all has anti-CO in various degree
2The corrosive effect, the anti-CO of 2# product
2Corrosive power is strong, and cement is good like the compactness of piece simultaneously, and gas permeability can reduce after corrosion.
CO
2Dividing potential drop: 5.0Mpa test period: 21 days
Test temperature: 110 ℃, 130 ℃, 150 ℃
Test-results sees Table 2.
As shown in Table 2, clean slurry does not prevent CO with adding
2The cement briquette of corrosive oil well cement additive is by CO
2Seriously corroded, the cement briquette ultimate compression strength after the corrosion reduces bigger, and gas permeability increases also big.No. 4 cement slurries that add the 2# admixture tie up to corrosion back cement briquette intensity and increase, and gas permeability reduces, and all has good anti-CO under the differing temps
2The corrosive performance.
Table 2
CO
2Pressure is 5.0Mpa, 130 ℃ of temperature, and etching time was respectively 21 days, 30 days, 40 days, 60 days.The results are shown in Table 3.
Table 3 result shows, along with the prolongation of etching time, adds the CO that prevents of the present invention
2The cement briquette of corrosive oil well cement additive is compared than the cement briquette that does not add this admixture, and the ultimate compression strength after the corrosion significantly increases, and the rate of permeation of cement annulated column also obviously reduces, and resistance to corrosion is better.
Table 3
CO
2Dividing potential drop: 5.0Mpa test period: 21 days
Test temperature: 130 ℃
The anti-CO of admixture under the different dosages
2Corrosive nature the results are shown in Table 4.
As seen from Table 4 along with the increase of admixture dosage, the anti-CO of mortar architecture
2The corrosive performance strengthens, and cement briquette compactness is good.
Table 4
Claims (5)
1. oil well cement additive that prevents carbon dioxide corrosion, it is characterized in that: described oil well cement additive includes the following component of content meter by weight percentage:
1. volcano grey matter mineral 20～65%wt
2. SILICA FUME 2～25%wt
3. aluminium salt mineral 5～25%wt
4. paraffin class organic materials 5～35%wt
5. methyl silicon sodium alcoholate 1～10%wt
6. slag 3～25%wt
The median size of the above aluminium salt mineral is 50～300nm; The median size of described paraffin class organic materials is 50～500nm.
2. the oil well cement additive that prevents carbon dioxide corrosion as claimed in claim 1 is characterized in that: described oil well cement additive includes the following component of percentage composition meter by weight:
1. volcano grey matter mineral 25～60%wt
2. SILICA FUME 5～20%wt
3. aluminium salt mineral 5～20%wt
4. paraffin class organic materials 10～30%wt
5. methyl silicon sodium alcoholate 3～8%wt
6. slag 5～20%wt.
3. as each described preparation method who prevents the oil well cement additive of carbon dioxide corrosion of claim 1～2, it is characterized in that may further comprise the steps:
(1) takes by weighing by described content and comprise described volcano grey matter mineral, SILICA FUME, aluminium salt mineral and slag, grind to puddle to mixture and reach 200 order fineness at least in interior component;
(2) mixture that step (1) is made and other comprise that the component of described paraffin class organic materials, methyl silicon sodium alcoholate puts into mixing machine by described content and mix, and after mixing, make the described oil well cement additive that prevents carbon dioxide corrosion.
4. as the described oil well cement additive application in the oil well cement well cementation that prevents carbon dioxide corrosion of each of claim 1～2, it is characterized in that be 100 parts by weight in well cementation with cement content in the grout, 15～60 parts of described oil well cement additives of carbon dioxide corrosion that prevent are added cementing slurry.
5. the application of oil well cement additive in the oil well cement well cementation that prevents carbon dioxide corrosion as claimed in claim 4, it is characterized in that be 100 parts by weight in well cementation with cement content in the grout, 15～45 parts of described oil well cement additives of carbon dioxide corrosion that prevent are added cementing slurry.
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Cited By (6)
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| CN103074044A (en) * | 2011-10-25 | 2013-05-01 | 中国石油化工股份有限公司 | Oil well cement additive used for preventing H2S/CO2 co-corrosion, and preparation method and application thereof |
| CN106336860A (en) * | 2015-07-07 | 2017-01-18 | 中国石油化工股份有限公司 | High temperature resistant anticorrosion oil well cement material, preparation method and application thereof |
| CN106747015A (en) * | 2017-01-03 | 2017-05-31 | 中国石油集团长城钻探工程有限公司固井公司 | One kind well cementation resistance to CO of high temperature resistance2Corrosion cement mortar |
| CN106966648A (en) * | 2017-03-10 | 2017-07-21 | 陕西省石油化工研究设计院 | A kind of anti-CO2、H2S corrodes cementing slurry |
| CN112573852A (en) * | 2019-09-27 | 2021-03-30 | 中国石油化工股份有限公司 | Preparation method of active silicon-aluminum oxide additive for oil well cement |
| CN112832714A (en) * | 2021-03-01 | 2021-05-25 | 陕西延长石油（集团）有限责任公司 | Method for preventing secondary damage of oil-gas well casing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103074044A (en) * | 2011-10-25 | 2013-05-01 | 中国石油化工股份有限公司 | Oil well cement additive used for preventing H2S/CO2 co-corrosion, and preparation method and application thereof |
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| CN106336860B (en) * | 2015-07-07 | 2020-01-17 | 中国石油化工股份有限公司 | High-temperature-resistant corrosion-resistant oil well cement material, preparation method and application |
| CN106747015A (en) * | 2017-01-03 | 2017-05-31 | 中国石油集团长城钻探工程有限公司固井公司 | One kind well cementation resistance to CO of high temperature resistance2Corrosion cement mortar |
| CN106966648A (en) * | 2017-03-10 | 2017-07-21 | 陕西省石油化工研究设计院 | A kind of anti-CO2、H2S corrodes cementing slurry |
| CN106966648B (en) * | 2017-03-10 | 2021-09-03 | 陕西省石油化工研究设计院 | CO prevention2、H2S corrosion well cementation cement slurry |
| CN112573852A (en) * | 2019-09-27 | 2021-03-30 | 中国石油化工股份有限公司 | Preparation method of active silicon-aluminum oxide additive for oil well cement |
| CN112832714A (en) * | 2021-03-01 | 2021-05-25 | 陕西延长石油（集团）有限责任公司 | Method for preventing secondary damage of oil-gas well casing |
| CN112832714B (en) * | 2021-03-01 | 2023-03-17 | 陕西延长石油（集团）有限责任公司 | Method for preventing secondary damage of oil-gas well casing |
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