CN106747015A - One kind well cementation resistance to CO of high temperature resistance2Corrosion cement mortar - Google Patents
One kind well cementation resistance to CO of high temperature resistance2Corrosion cement mortar Download PDFInfo
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- CN106747015A CN106747015A CN201710001866.8A CN201710001866A CN106747015A CN 106747015 A CN106747015 A CN 106747015A CN 201710001866 A CN201710001866 A CN 201710001866A CN 106747015 A CN106747015 A CN 106747015A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/22—Carbonation resistance
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
One kind well cementation resistance to CO of high temperature resistance2Corrosion cement mortar, by weight, including：100 parts of cement；1~10 part of fluid loss agent；0~8 part of retarder；0~1 part of defoamer；20~60 parts of water.Behavior of Hardened Cement Paste of the invention is in equal hot conditions and CO2Under etching condition, high temperature resistance and resistance to CO2Corrosive power is excellent, and cement mortar traditional performance meets site operation requirement, has broad application prospects.
Description
Technical field
The present invention relates to cementing concrete field, more particularly it relates to a kind of well cementation resistance to CO of high temperature resistance2Corrosive water
Mud.
Background technology
With the exhaustion of conventional gas and oil resource exploitation, each elephant of China has come into secondary, tertiary oil recovery period.It is thick
Oil has great extraction value as a kind of non-conventional oil resource.Combustion in situ oil recovery technique have developed rapidly in recent years
A kind of oil recovery by heating method with obvious technical advantage and potentiality, is one of technology of raising thick oil recovery ratio, and its principle is just
It is, by the use of the heavy component in in-place oil as fuel, by the use of air or oxygen rich gas as combustion adjuvant, to take spontaneous combustion and people
The methods such as work igniting make reservoir temperature reach crude oil burning-point, and are continuously injected into combustion adjuvant, make Crude Oil sustained combustion, and burning is anti-
Substantial amounts of heat, heated oil reservoir should be produced so that reservoir temperature rises 500~700 DEG C, and heavy component is cracked at high temperature, injection
Gas, heavy oil pyrolysis generation light oil, burning generation gas and water vapour be used for drive crude oil to producing well flow,
And produced from producing well.
In fireflood heavy crude heat extraction, underground and stratum produce up to more than 500 DEG C of high temperature, and produced with burning
CO2Gas, high temperature resistant and anti-CO to Behavior of Hardened Cement Paste2Corrosion has requirement higher.The intensity meeting under the high temperature conditions of silicate cement mudstone
Deep fades, experiment shows that silicate cement mudstone occurs obvious cracking phenomena at 500 DEG C.Aluminate cement is considered as
It is conventional high-temperature cement, but in this temperature range, there is also strength retrogression's phenomenon, while the anti-CO of drated calcium aluminate2It is rotten
Corrosion can not be good.Phosphate cement has excellent anti-CO2Corrosive nature, but because the cement system does not have heat-resisting quantity
Can, obvious cracking phenomena occurs under the high temperature conditions.It would therefore be highly desirable to develop a kind of resistance to CO of well cementation high temperature resistance2Corrosion
Cement mortar solves the above problems.
The content of the invention
In order to solve the above problems, the invention provides a kind of well cementation resistance to CO of high temperature resistance2Corrosion cement mortar.
In order to realize foregoing invention purpose, this invention takes following technical scheme：
One kind well cementation resistance to CO of high temperature resistance2Corrosion cement mortar, by weight, including：
As a kind of perferred technical scheme, by weight, including：
As a kind of perferred technical scheme, the cement, by weight, including：
As a kind of perferred technical scheme, the cement, by weight, including：
As a kind of perferred technical scheme, described phosphate is sodium phosphate, sodium polyphosphate, sodium dihydrogen phosphate, six
Any one or a few combination in sodium metaphosphate, ammonium hydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate.
As a kind of perferred technical scheme, described alumina powder is micro- to calcine Alpha-alumina, schmigel, aluminum oxide
Any one or a few combination in powder, Reactive alumina.
As a kind of perferred technical scheme, described resistant material is appointing in blast-furnace cinder, flyash, diatomite
Anticipate the combination of one or more.
As a kind of perferred technical scheme, described fluid loss agent be the-α containing acrylamide and acrylic acid-acrylamide-
2- methyl propane sulfonic acid copolymers.
As a kind of perferred technical scheme, described retarder is citric acid, tartaric acid, boric acid, sodium tetraborate, Portugal heptan
Any one or a few combination in saccharic acid.
As a kind of perferred technical scheme, described defoamer organic silicon defoamer.
Specific embodiment
The participation in the election detailed description for being preferable to carry out method of the invention below and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, all terms used herein (including technology art
Language and scientific terminology) have with art of the present invention in those of ordinary skill general understanding identical meaning.Should also
Understand, those terms defined in such as general dictionary should be understood that the meaning having with the context of prior art
The consistent meaning of justice, and unless defined as here, will not be with idealizing or excessively formal implication be explained.
One kind well cementation resistance to CO of high temperature resistance2Corrosion cement mortar, by weight, including：
As a kind of perferred technical scheme, by weight, including：
Cement
Cement of the present invention is aluminate cement, phosphate, alumina powder, resistant material mechanical mixture are formed,
As a kind of perferred technical scheme, the cement, by weight, including：
As a kind of further preferred technical scheme, the cement, by weight, including：
Aluminate cement
Aluminate cement is with Al2O3、CaO、SiO2It is main component, because three kinds of ratios of main component are different, cement is ripe
The composition of material is also different, mainly there is monocalcium aluminate (CA), calcium dialuminate (CA2), C 12 A 7 (C12A7), calcium aluminium it is yellow long
Stone (C2AS), six monocalcium aluminate (CA6)。
The maximum feature of aluminate cement is to develop by force very fast, can almost reach the 80% of maximum intensity in 24h.
In addition, (5~10 DEG C) can also be hardened well at low temperature, but its strength development is very big with curing temperature, ratio of mud relation, water
The crystal transfer for changing product will also cause strength retraction：Aluminate cement hydrated product at low temperatures and high temperatures is different.30
Below DEG C temperature, hydrated product is mainly CAH10And C2AH8, both belong to hexagonal crystal system, and the sheet and needle-like for being formed are brilliant
Body is crossed one another overlap joint, forms firm skeleton structure, and gel aluminum hydroxide is filled therebetween, and combined water is big, therefore hole
Rate is low, compact structure, cement is obtained mechanical strength higher.After extension over time or temperature are higher than 30 DEG C, CAH10
And C2AH8The cubic crystal C of stabilization can be progressively transformed into3AH6, not only decline the bond strength between crystal, more serious making is solid
Phase volume significantly reduces, and porosity is increased considerably, so that the reduction of aluminate cement concrete strength.Meanwhile, because water
There are more aluminium hydroxide, the resistance to CO of Behavior of Hardened Cement Paste in change product2Corrosive nature is poor.
(2m+n)CA+(10n+11m)H→nCAH10+mC2AH8+mAH3((low temperature)
3CA+12H→C3AH6+2AH3(high temperature)
Phosphate
Phosphate of the present invention preferably is selected from sodium phosphate, sodium polyphosphate, sodium dihydrogen phosphate, calgon, phosphoric acid hydrogen
Any one or a few combination in ammonium, potassium phosphate, potassium dihydrogen phosphate.More preferably calgon.
Alumina powder
Alumina powder of the present invention preferably is selected from as calcining Alpha-alumina, schmigel, alumina powder, activated alumina are micro-
Any one or a few combination in powder, more preferably calcines α-Al2Any one or two kinds in O or white fused alumina
Combination.
Resistant material
Resistant material of the present invention preferably is selected from any one or a few in blast-furnace cinder, flyash, diatomite
Combination, more preferably any one in blast-furnace cinder or flyash or two kinds of combination.
Fluid loss agent
During note is replaced, because dynamic filtration is larger, the annular space slurry ratio of mud is reduced cement mortar, causes cement slurry density to increase
Plus, rheological property is deteriorated, and the thickening time shortens, and denseness is sharply increased in a short time, and cause cement mortar to be noted increases for pump pressure, has
When also have cause beat solid cannula and cementing job failure danger；In cement mortar condensation process, the larger cement of dehydration
Slurry can also form bridge blinding in narrow annular space, pressure on oil, gas-bearing formation be acted on so as to reduce fluid column, while can also be in cement
Interior formation micro-capillary channel, causes profit has channeling problem.Therefore additional such as fluid loss agent is needed to avoid the generation of problems.
Fluid loss agent is preferably the-α containing acrylamide and acrylic acid-acrylamide-2-methyl propane sulfonic copolymer in the present invention
Or one or two in modified cellulose.
Fluid loss agent acrylamide and acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymer is had by Great Wall drilling project
Cementer of limit company produces, and trade name is GWF-500L.
It is commonly used for the various cellulose etherses of cement filter loss-reducing agent for oil well, including carboxymethylcellulose calcium (CMC), ethoxy fibre
Dimension plain (HEC), carboxymethyl hydroxyethyl cellulose (CMHEC) etc..Cellulose ethers material has good filtrate loss controllability, passes through
Increasing or decreasing its consumption always can be by the Filtrate Loss Control of cement mortar in certain scope.But cellulosic material plus
Enter, the denseness of cement mortar can be made excessive, cause to stir and pump very difficult, such material is also existing with certain extra retarded set
As cement mortar can not in time solidify in underground, influence production.
Modified cellulose
In order to the addition for solving fiber can make the denseness of cement mortar excessive, cause to stir and pump very difficult, such material
Material also with certain extra retarded set phenomenon problem, the present inventor pass through experimental results demonstrate treatment is modified to cellulose can
To solve the above problems.Modified cellulose of the present invention refer to maleic anhydride modified cellulose or with acrylic acid to Malaysia
Cellulose after anhydride modified be further modified obtained from both products as precipitation agent, imitated with excellent precipitation
Really.
Maleic anhydride modified cellulose
Take in appropriate maleic anhydride addition reactor, DMF is added under stirring, stirring is equal
The ethyl cellulose after dried process is added after even according to a certain ratio, is sufficiently mixed uniformly, dried in air dry oven.Will
Uniform drying mixture is transferred in reactor, and suitable reaction temperature is controlled under the conditions of nitrogen environmental protection, oil bath heating, reaction
Certain hour.Synthetic sample carries out extracting reaction 24 hours using Soxhlet extractor by extract of acetone soln, extracts product
Freeze-day with constant temperature extremely can constant weight in vacuum drying chamber.
It is acrylic acid modified it is maleic anhydride modified after cellulose
The present invention be it is described it is acrylic acid modified maleic anhydride modified after cellulose refer to formerly to carry out maleic anhydride to change
After the work of property cellulose, product is taken, then it is further modified with acrylic acid.
The solution reaction of the cellulose after acrylic acid and modified maleic anhydride modification is carried out at 100 DEG C.Reactor is 1L
Equipped with magnetic seal agitator and temperature, pressure, speed probe PARR5111 autoclaves, circulated using high temperature oil bath
Hydraulic plunger pump carries out sample introduction during equipment carries out the Grad10 types of temperature control, Shanghai Tauto Biotechnology Co., Ltd..Maleic acid
Cellulose solution after anhydride modification is all added in reactor before the reaction, and reactor is purged with nitrogen, uses nitrogen pressurize, rapidly
Heat up, after after temperature stabilization, acrylic acid aqueous solution and aqueous hydrogen peroxide solution are at the uniform velocity added dropwise by hydrodynamic injection pump respectively, be added dropwise
All terminate the follow-up warm stirring reaction of continuation of insurance, fast cooling is simultaneously discharged gas reactor and terminates reaction, is obtained final product.
Maleic anhydride modified cellulose is taken in the present invention, because there is the maleic anhydride introduced in molecule absorption interface to live
Property agent particulate electrostatic repulsion forces and steric hindrance effect, improve drop dehydration effect.The present inventor attempts using acrylic acid
Cellulose after modified maleic anhydride modification learns that this kind of fluid loss agent can control aluminophosphates as fluid loss agent by experiment
Cement mortar API dehydrations are less than 50mL, while the performance such as rheological characteristic and thickening time to cement mortar is without considerable influence, along with water
The carrying out of mud hydration reaction, the surface state of particle is changed, the effect for lifting drop dehydration, and undue increasing will not be caused again
Thick effect, solves the addition of traditional fibre cellulosic material, and the denseness of cement mortar can be made excessive, causes to stir and pump very tired
Difficulty, such material also has certain extra retarded set phenomenon, and cement mortar can not in time solidify in underground, influences the problem of production, and
The resistance to CO of high temperature resistance of cement of the present invention can be strengthened on certain depth2Corrosive nature.
The well cementation resistance to CO of high temperature resistance that the present invention is provided2Corrosion cement mortar API fluid losses are controllable, and the thickening time is adjustable, drop
Dehydration effect is excellent, and Binder Materials is ultimately formed through aquation.The Binder Materials intensity can not wane under 550 DEG C of hot conditions
Move back, while the Binder Materials will not be by CO2Corrosion.Therefore, the application cement mortar has good high temperature resistant property and resistance to CO2It is rotten
Corrosion energy, after tested the Behavior of Hardened Cement Paste through 550 DEG C of high temperature sections after a while, cement strength increases to 17.9MPa by 16.3MPa, 120
℃、5MPa CO2Etching extent is less than the 10% of API G class g cements in environment.
Retarder
Retarder of the present invention is any one in citric acid, tartaric acid, boric acid, sodium tetraborate, glucoheptonic acid
Or several combinations, preferably any one in citric acid or tartaric acid or two kinds of combination.Retarder of the present invention
Cement slurry thickening time can effectively be extended, and dosage is insensitive, is less prone to extra retarded set phenomenon.Retarder is by Great Wall drilling project
Cementer of Co., Ltd produces, and trade name is GWR-500S.
Defoamer
Defoamer of the present invention preferably is selected from organic silicon defoamer, and-Si-O is contained more preferably in molecular structure
With-CH3The defoamer of group.Defoamer is produced by Great Wall cementer of drilling project Co., Ltd, and trade name is GWX-1L.
Dry ash component described in following examples includes aluminate cement, phosphate, alumina powder, resistant material.
The mixed component of water includes fluid loss agent, retarder, defoamer.
With reference to specific embodiment, the present invention is described in further detail.
It is commercially available that raw material of the present invention does not have specified otherwise to be.
Embodiment 1
Cement dry ash component is taken respectively：Aluminate cement 100g, sodium phosphate 5g, calcine Alpha-alumina 30g, blast-furnace cinder
10g mechanical mixtures are uniform.
Fetch water respectively and mix component：Acrylamide and acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymer 1 g, citric acid
1g, LY-401 defoamer 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T
19139-2003 prepares cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides
Running water.
Embodiment 2
Cement dry ash component aluminate cement 100g, sodium polyphosphate 10g, white fused alumina 30g, flyash 30g machines are taken respectively
Tool is well mixed.
Fetch water respectively and mix component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymers 2g, tartaric acid
2g, LY-401 defoamer 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T
19139-2003 prepares cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides
Running water.
Embodiment 3
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 15g, alumina powder 40g, diatomite are taken respectively
30g mechanical mixtures are uniform.
Fetch water respectively mixed component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymers 3g, boric acid 3g,
LY-401 defoamers 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T
19139-2003 prepares cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides
Running water.
Embodiment 4
Cement dry ash component aluminate cement 100g, calgon 20g, Reactive alumina 50g, blast furnace are taken respectively
Slag 50g mechanical mixtures are uniform.
Fetch water respectively and mix component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymers 4g, tetraboric acid
Sodium 2g, LY-401 defoamer 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/
T 19139-2003 prepare cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government carries
It is provided from water.
Embodiment 5
Cement dry ash component aluminate cement 100g, ammonium hydrogen phosphate 20g are taken respectively, calcine Alpha-alumina 50g, flyash
50g mechanical mixtures are uniform.
Fetch water respectively and mix component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymers 5g, tetraboric acid
Sodium 2g, LY-401 defoamer 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/
T 19139-2003 prepare cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government carries
It is provided from water.
Embodiment 6
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g calcining α-oxygen is taken respectively
Change aluminium 50g, flyash 50g mechanical mixtures are uniform.
Fetch water respectively and mix component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymer 1s 0g, tartaric acid
2g, LY-401 defoamer 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T
19139-2003 prepares cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides
Running water.
Embodiment 7
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g calcining α-oxygen is taken respectively
Change aluminium 50g, flyash 50g mechanical mixtures are uniform.
Fetch water respectively and mix component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymer 1s 0g, tartaric acid
2g, LY-401 defoamer 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T
19139-2003 prepares cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides
Running water.
Embodiment 8
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g are taken respectively, calcine α-oxygen
Change aluminium 25g, alumina powder 25g, flyash 15g, blast-furnace cinder 15g mechanical mixtures are uniform.
Fetch water respectively and mix component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymers 8g, citric acid
4g, LY-401 defoamer 0.2g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T
19139-2003 prepares cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides
Running water.
Embodiment 9
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, sodium phosphate 15g, alumina powder are taken respectively
15g, Reactive alumina 20g, flyash 10g, blast-furnace cinder 25g mechanical mixtures are uniform.
Fetch water respectively and mix component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymers 8g, citric acid
5g, LY-401 defoamer 0.2g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T
19139-2003 prepares cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides
Running water.
Embodiment 10
Cement dry ash component aluminate cement 100g, sodium polyphosphate 15g, potassium dihydrogen phosphate 20g are taken respectively, calcine α-oxygen
Change aluminium 15g, Reactive alumina 15g, flyash 10g, diatomite 15g mechanical mixtures are uniform.
Fetch water respectively and mix component acryl acid amides-acrylic acid-α-acrylamide-2-methyl propane sulfonic copolymer 1s 0g, glucoheptose
Sour 5g, LY-401 defoamer 0.2g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/
T 19139-2003 prepare cement mortar and maintenance Behavior of Hardened Cement Paste, and Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government carries
It is provided from water.
Embodiment 11
Cement dry ash component is taken respectively：Aluminate cement 100g, sodium phosphate 5g, calcine Alpha-alumina 30g, blast-furnace cinder
10g mechanical mixtures are uniform.
Fetch water respectively and mix component：Maleic anhydride modified cellulose 1g, citric acid 1g, LY-401 defoamer 0.1g.Take mixing
Good dry ash component 100g mixes component with above-mentioned water, using with pulp-water, cement mortar and maintenance is prepared according to GB/T 19139-2003
Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Maleic anhydride modified cellulose
Take in 2g maleic anhydrides addition reactor, 100mL DMFs are added under stirring, stir
After mixing uniformly, the 10g ethyl celluloses after dried process are added, be sufficiently mixed uniformly, dried in air dry oven at 50 DEG C
10h.Uniform drying mixture is transferred in reactor, under nitrogen environmental protection, 80 DEG C of heating conditions of oil bath, 2.5h is reacted.Close
Carry out extracting reaction 24 hours by extract of acetone soln using Soxhlet extractor into sample, extract product in vacuum drying chamber
Middle freeze-day with constant temperature is obtained final product to meeting constant weight.
Embodiment 12
Cement dry ash component aluminate cement 100g, sodium polyphosphate 10g, white fused alumina 30g, flyash 30g machines are taken respectively
Tool is well mixed.
The maleic anhydride modified cellulose 2g of mixed component of fetching water respectively, tartaric acid 2g, LY-401 defoamer 0.1g.Take and mix
Dry ash component 100g and the mixed component of above-mentioned water, using with pulp-water, cement mortar and curing water are prepared according to GB/T 19139-2003
Mudstone, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
Embodiment 13
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 15g, alumina powder 40g, diatomite are taken respectively
30g mechanical mixtures are uniform.
The maleic anhydride modified cellulose 3g of mixed component of fetching water respectively, boric acid 3g, LY-401 defoamer 0.1g.Take what is mixed
Dry ash component 100g mixes component with above-mentioned water, using with pulp-water, cement mortar and maintenance cement is prepared according to GB/T 19139-2003
Stone, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
Embodiment 14
Cement dry ash component aluminate cement 100g, calgon 20g, Reactive alumina 50g, blast furnace are taken respectively
Slag 50g mechanical mixtures are uniform.
The maleic anhydride modified cellulose 4g of mixed component of fetching water respectively, sodium tetraborate 2g, LY-401 defoamer 0.1g.Take mixing
Good dry ash component 100g mixes component with above-mentioned water, using with pulp-water, cement mortar and maintenance is prepared according to GB/T 19139-2003
Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
Embodiment 15
Cement dry ash component aluminate cement 100g, ammonium hydrogen phosphate 20g are taken respectively, calcine Alpha-alumina 50g, flyash
50g mechanical mixtures are uniform.
The maleic anhydride modified cellulose 5g of mixed component of fetching water respectively, sodium tetraborate 2g, LY-401 defoamer 0.1g.Take mixing
Good dry ash component 100g mixes component with above-mentioned water, using with pulp-water, cement mortar and maintenance is prepared according to GB/T 19139-2003
Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
Embodiment 16
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g calcining α-oxygen is taken respectively
Change aluminium 50g, flyash 50g mechanical mixtures are uniform.
The maleic anhydride modified cellulose 10g of mixed component of fetching water respectively, tartaric acid 2g, LY-401 defoamer 0.1g.Take mixing
Good dry ash component 100g mixes component with above-mentioned water, using with pulp-water, cement mortar and maintenance is prepared according to GB/T 19139-2003
Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
Embodiment 17
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g calcining α-oxygen is taken respectively
Change aluminium 50g, flyash 50g mechanical mixtures are uniform.
The maleic anhydride modified cellulose 10g of mixed component of fetching water respectively, tartaric acid 2g, LY-401 defoamer 0.1g.Take mixing
Good dry ash component 100g mixes component with above-mentioned water, using with pulp-water, cement mortar and maintenance is prepared according to GB/T 19139-2003
Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
Embodiment 18
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g are taken respectively, calcine α-oxygen
Change aluminium 25g, alumina powder 25g, flyash 15g, blast-furnace cinder 15g mechanical mixtures are uniform.
The maleic anhydride modified cellulose 8g of mixed component of fetching water respectively, citric acid 4g, LY-401 defoamer 0.2g.Take and mix
Dry ash component 100g and the mixed component of above-mentioned water, using with pulp-water, cement mortar and curing water are prepared according to GB/T 19139-2003
Mudstone, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
Embodiment 19
Cement dry ash component is taken respectively：Aluminate cement 100g, sodium phosphate 5g, calcine Alpha-alumina 30g, blast-furnace cinder
10g mechanical mixtures are uniform.
Fetch water respectively and mix component：It is acrylic acid modified it is maleic anhydride modified after cellulose 1g, citric acid 1g, LY-401 froth breaking
Agent 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T 19139-2003 systems
Standby cement mortar and maintenance Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste are conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
It is acrylic acid modified it is maleic anhydride modified after cellulose
Cellulose solution after 2g is maleic anhydride modified is all added in reactor before the reaction, and reactor is purged with nitrogen
After 30 minutes, with nitrogen pressurize about 2atm, it is brought rapidly up to 120 DEG C, after after temperature stabilization, is distinguished at the uniform velocity by hydrodynamic injection pump
50ml acrylic acid aqueous solutions and aqueous hydrogen peroxide solution is added dropwise, is added dropwise and the warm stirring reaction of follow-up continuation of insurance all terminate 2 hours, quickly
Lower the temperature and discharge gas reactor and terminate reaction, obtain final product.
Embodiment 20
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 15g, alumina powder 40g, diatomite are taken respectively
30g mechanical mixtures are uniform.
Water intaking respectively mixes cellulose 3g, boric acid 3g, LY-401 defoamer after part acrylic modified maleic anhydride modification
0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, water is prepared according to GB/T19139-2003
Mud and maintenance Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste are conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
It is acrylic acid modified it is maleic anhydride modified after cellulose preparation method with reference to embodiment 19.
Embodiment 21
Cement dry ash component aluminate cement 100g, ammonium hydrogen phosphate 20g are taken respectively, calcine Alpha-alumina 50g, flyash
50g mechanical mixtures are uniform.
Cellulose 5g respectively after the mixed part acrylic modified maleic anhydride modification of water intaking, sodium tetraborate 2g, LY-401 disappear
Infusion 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T 19139-2003
Cement mortar and maintenance Behavior of Hardened Cement Paste are prepared, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
It is acrylic acid modified it is maleic anhydride modified after cellulose preparation method with reference to embodiment 19.
Embodiment 22
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g calcining α-oxygen is taken respectively
Change aluminium 50g, flyash 50g mechanical mixtures are uniform.
Water intaking respectively mixes cellulose 10g, tartaric acid 2g, LY-401 froth breaking after part acrylic modified maleic anhydride modification
Agent 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T 19139-2003 systems
Standby cement mortar and maintenance Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste are conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
It is acrylic acid modified it is maleic anhydride modified after cellulose preparation method with reference to embodiment 19.
Embodiment 23
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g calcining α-oxygen is taken respectively
Change aluminium 50g, flyash 50g mechanical mixtures are uniform.
Water intaking respectively mixes cellulose 10g, tartaric acid 2g, LY-401 froth breaking after part acrylic modified maleic anhydride modification
Agent 0.1g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, according to GB/T 19139-2003 systems
Standby cement mortar and maintenance Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste are conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
It is acrylic acid modified it is maleic anhydride modified after cellulose preparation method with reference to embodiment 19.
Embodiment 24
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g are taken respectively, calcine α-oxygen
Change aluminium 25g, alumina powder 25g, flyash 15g, blast-furnace cinder 15g mechanical mixtures are uniform.
Water intaking respectively mixes cellulose 8g, citric acid 4g, LY-401 froth breaking after part acrylic modified maleic anhydride modification
Agent 0.2g.Take the dry ash component 100g for mixing and mix component with above-mentioned water, using with pulp-water, prepared according to GB/T19139-2003
Cement mortar and maintenance Behavior of Hardened Cement Paste, Behavior of Hardened Cement Paste are conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
It is acrylic acid modified it is maleic anhydride modified after cellulose preparation method with reference to embodiment 19.
Embodiment 25
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g are taken respectively, calcine α-oxygen
Change aluminium 25g, alumina powder 25g, flyash 15g, blast-furnace cinder 15g mechanical mixtures are uniform.
Water intaking respectively mixes cellulose 6g, the maleic anhydride modified cellulose after part acrylic modified maleic anhydride modification
2g, citric acid 4g, LY-401 defoamer 0.2g.The dry ash component 100g that mixes and the mixed component of above-mentioned water are taken, using with pulp-water,
Cement mortar and maintenance Behavior of Hardened Cement Paste are prepared according to GB/T 19139-2003, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.It is with pulp-water
Municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
It is acrylic acid modified it is maleic anhydride modified after cellulose preparation method with reference to embodiment 19.
Embodiment 26
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g are taken respectively, calcine α-oxygen
Change aluminium 25g, alumina powder 25g, flyash 15g, blast-furnace cinder 15g mechanical mixtures are uniform.
Water intaking respectively mixes cellulose 4g, the maleic anhydride modified cellulose after part acrylic modified maleic anhydride modification
6g, citric acid 4g, LY-401 defoamer 0.2g.The dry ash component 100g that mixes and the mixed component of above-mentioned water are taken, using with pulp-water,
Cement mortar and maintenance Behavior of Hardened Cement Paste are prepared according to GB/T 19139-2003, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.It is with pulp-water
Municipal government provides running water.
Maleic anhydride modified cellulose is with reference to embodiment 11.
It is acrylic acid modified it is maleic anhydride modified after cellulose preparation method with reference to embodiment 19.
Comparative example 1
Sulfur resistive high (HSR) G class g cements of API G grades of oil-well cement oil Fushun Cement Factory production, 100g.
Comparative example 2
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g are taken respectively, calcine α-oxygen
Change aluminium 25g, alumina powder 25g, flyash 15g, blast-furnace cinder 15g mechanical mixtures are uniform.
Fetch water mixed component carboxymethylcellulose calcium 6g, citric acid 4g, LY-401 defoamer 0.2g respectively.Take the dry ash for mixing
Component 100g mixes component with above-mentioned water, using with pulp-water, cement mortar and maintenance Behavior of Hardened Cement Paste is prepared according to GB/T 19139-2003,
Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Comparative example 3
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g are taken respectively, calcine α-oxygen
Change aluminium 25g, alumina powder 25g, flyash 15g, blast-furnace cinder 15g mechanical mixtures are uniform.
Fetch water mixed component carboxymethyl hydroxyethyl cellulose 8g, citric acid 4g, LY-401 defoamer 0.2g respectively.Take and mix
Dry ash component 100g and the mixed component of above-mentioned water, using with pulp-water, cement mortar and curing water are prepared according to GB/T 19139-2003
Mudstone, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Comparative example 4
Cement dry ash component aluminate cement 100g, sodium dihydrogen phosphate 20g, calgon 15g are taken respectively, calcine α-oxygen
Change aluminium 25g, alumina powder 25g, flyash 15g, blast-furnace cinder 15g mechanical mixtures are uniform.
Fetch water mixed component carboxylic hydroxyethyl cellulose 4g, citric acid 4g, LY-401 defoamer 0.2g respectively.Take mix dry
Grey component 100g mixes component with above-mentioned water, using with pulp-water, cement mortar and maintenance cement is prepared according to GB/T 19139-2003
Stone, Behavior of Hardened Cement Paste is conserved 3 days under specified requirements.With pulp-water for municipal government provides running water.
Performance test
The Behavior of Hardened Cement Paste prepared to above-described embodiment and comparative example cement-slurry method is commented under the conditions of specified temperature (550 DEG C)
Valency its high temperature resistant property.High temperature resistant property evaluation result such as table 1.
Resistance to CO2Corrosive nature is tested, and is 120 DEG C, CO in etching condition2Partial pressure is 5MPa.The theoretical foundation of the experiment is
CO2The product for corroding Behavior of Hardened Cement Paste is calcium carbonate, and the decomposition temperature of calcium carbonate is 600-770 DEG C, therefore Behavior of Hardened Cement Paste is in 600-770
DEG C weight loss then for corrosion product Decomposition of Calcium Carbonate CO2Quality.Behavior of Hardened Cement Paste is measured by thermogravimetric analysis means in the temperature
Interval weight loss is spent, Behavior of Hardened Cement Paste CO under given conditions is characterized2Corrosion condition, sample is bigger in the interval weight loss,
Then show that sample is easier by CO2Corrosion, otherwise then more resistance to CO2Corrosion, resistance to CO2Evaluation of Corrosion Resistance result such as table 2.
Cement mortar traditional performance evaluation test result is as shown in table 3.
The high temperature resistant property evaluation table result of table 1
The resistance to CO of table 22Evaluation of Corrosion Resistance
The resistance to CO of high temperature resistance of the present invention2Corrosion cement mortar is notable in extent of corrosion under equal conditions and permeability
It is superior to cement mortar in comparative example.
The cement mortar traditional performance of table 3 is evaluated
The resistance to CO of high temperature resistance that the present invention is provided2Corrosion cement mortar traditional performance can meet site operation and be smoothed out, and drop
Dehydration agent can effectively control cement mortar API dehydrations less than 50mL, and retarder can effectively extend the resistance to CO of high temperature resistance2Corrosion cement mortar is thick
The change time (without the cement slurry thickening time ＜ 30min of retarder).
To sum up table 1, the test result in 2,3, show the resistance to CO of high temperature resistance of present invention offer2Corrode the high temperature resistant of cement mortar
And resistance to CO2Corrosive nature is superior to every cement described in comparative example.
Claims (10)
1. it is a kind of to cement the well with the resistance to CO of high temperature resistance2Corrosion cement mortar, it is characterised in that by weight, including：
2. it is according to claim 1 to cement the well with the resistance to CO of high temperature resistance2Corrosion cement mortar, it is characterised in that by weight, bag
Include：
3. it is according to claim 1 and 2 to cement the well with the resistance to CO of high temperature resistance2Corrosion cement mortar, it is characterised in that the cement, presses
Weight portion meter, including：
4. it is according to claim 3 to cement the well with the resistance to CO of high temperature resistance2Corrosion cement mortar, it is characterised in that the cement, by weight
Amount part meter, including：
5. the resistance to CO of high temperature resistance of the well cementation according to claim 3 or 42Corrosion cement mortar, it is characterised in that described phosphoric acid
Salt is appointing in sodium phosphate, sodium polyphosphate, sodium dihydrogen phosphate, calgon, ammonium hydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate
Anticipate the combination of one or more.
6. the resistance to CO of high temperature resistance of the well cementation according to claim 3 or 42Corrosion cement mortar, it is characterised in that described oxidation
Aluminium powder is to calcine any one or a few the combination in Alpha-alumina, schmigel, alumina powder, Reactive alumina.
7. the resistance to CO of high temperature resistance of the well cementation according to claim 3 or 42Corrosion cement mortar, it is characterised in that described corrosion resistant
Corrosion material is any one or a few the combination in blast-furnace cinder, flyash, diatomite.
8. it is according to claim 1 and 2 to cement the well with the resistance to CO of high temperature resistance2Corrosion cement mortar, it is characterised in that described drop is lost
Aqua is the-α containing acrylamide and acrylic acid-acrylamide-2-methyl propane sulfonic copolymer.
9. it is according to claim 1 and 2 to cement the well with the resistance to CO of high temperature resistance2Corrosion cement mortar, it is characterised in that described slow setting
Agent is any one or a few the combination in citric acid, tartaric acid, boric acid, sodium tetraborate, glucoheptonic acid.
10. it is according to claim 1 and 2 to cement the well with the resistance to CO of high temperature resistance2Corrosion cement mortar, it is characterised in that described froth breaking
Agent is organic silicon defoamer.
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| CN111138160A (en) * | 2020-01-02 | 2020-05-12 | 天津中油渤星工程科技有限公司 | H2S corrosion-resistant cement, preparation method and application thereof, and well cementation cement sheath |
| CN115043621A (en) * | 2022-03-29 | 2022-09-13 | 中海石油(中国)有限公司深圳分公司 | High-density cement slurry resistant to high temperature and carbon dioxide corrosion and preparation method and application thereof |
| CN116283164A (en) * | 2023-03-14 | 2023-06-23 | 中国石油大学(华东) | High-temperature-resistant well cementation material and preparation method and application thereof |
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| CN109516745A (en) * | 2017-09-18 | 2019-03-26 | 中国石油天然气集团公司 | Cement paste for well cementation and preparation method thereof |
| CN111138160A (en) * | 2020-01-02 | 2020-05-12 | 天津中油渤星工程科技有限公司 | H2S corrosion-resistant cement, preparation method and application thereof, and well cementation cement sheath |
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