CN107559010B - A kind of well-cementing cement - Google Patents
A kind of well-cementing cement Download PDFInfo
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Abstract
The invention discloses a kind of well-cementing cements, belong to bored material technical field.It is digested after chitosan is swollen, and it is mixed with polyacrylamide, additive is made, by rice hull cellulose low-temperature carbonization, obtain doughnut, and doughnut is impregnated in isocyanates, termination process is carried out again, modified fibre is made, according to parts by weight, successively weigh 50~70 parts of cement, 20~25 parts of silicon powders, 20~30 parts of water, 10~15 parts of additives, 12~18 parts of modified fibres, 2~5 parts of dispersing agents, 10~15 parts of slags and 10~12 parts of filler materials, after cement is mixed with water, sequentially add silicon powder, additive, modified fibre, dispersing agent, slag, glutaraldehyde and filler material, it is stirred, it vibrates molding, after conserving, obtain well-cementing cement.Well-cementing cement prepared by the present invention has excellent mechanical property and anti-corrosion property energy.
Description
Technical field
The invention discloses a kind of well-cementing cements, belong to bored material technical field.
Background technique
In cementing operation, cementing slurry will be subjected to underground ring by the annular space between sprue bushing and stratum, cement slurry
Border and finally solidify to form the cement sheath with certain cementing power and hardness.In well cement sheath have effectively packing stratum and
It supports, the function of protection sleeve pipe.For stable yields, volume increase, the raisings such as each oil field all filled the water in succession, pressure break, acidification, perforations adding are raw
Producing undergrounds engineer operation, the different operation process such as pressure difference necessarily makes borehole condition change, and casing internal pressure changes, stratum is enclosed
The effects of temperature stress caused by rock pressure change and wellbore temperatures change, cement sheath stress is made to change, it may
Cause cement sheath to crack, or even the packing of cement sheath can be made to act on failure, cause channelling between underground oil and gas water layer and
The corrosion failure of casing, causes oil well to scrap when serious.Therefore, well-cementing cement mechanical property is studied, cement ring body is improved
Integrality have great importance to production and the long term life of oil-water well.Studies have shown that fiber can improve cement-based material
Mechanical property.Common fiber includes polyester fiber, polypropylene fibre, carbon fiber etc. in well cementation at present, has one to Behavior of Hardened Cement Paste
Fixed toughening effect, but have the shortcomings that bad dispersibility, at high cost or durability are poor.
Oil field enters the middle and later periods, and with the implementation of the development stimulations such as water filling, acidification, pressure break, thermal recovery, high pressure easily makes in well
Behavior of Hardened Cement Paste generates non-plastic fracture, causes oil gas water channeling, water flooding can destroy water mudrock structure to the corrosion of Behavior of Hardened Cement Paste, due to corruption
Medium is lost to the corrosion and damage of oil gas casing, and payzone oil gas water breakthrough is serious.Behavior of Hardened Cement Paste non-plastic fracture and water flooding are to Behavior of Hardened Cement Paste
Corrosion can all seriously affect oil/gas well Production Life.Water-soluble erosion and ion exchange erosion be Behavior of Hardened Cement Paste by the main reason for corrosion it
One, increasing Behavior of Hardened Cement Paste compactness and reducing a possibility that hydrolysis product of cement is occurred by corrosion and ion exchange is to mention
The high corrosion resistant main path of Behavior of Hardened Cement Paste.
Therefore, how to improve well-cementing cement mechanical property and the bad disadvantage of corrosion resistance, it is higher comprehensive to obtain
The well-cementing cement of energy is that it is promoted and is applied to broader field, meets industrial production demand urgent problem to be solved.
Summary of the invention
The present invention solves the technical problem of: it is bad for traditional well-cementing cement mechanical property and corrosion resistance
Disadvantage provides a kind of well-cementing cement.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of well-cementing cement is made of the raw material of following parts by weight:
50~70 parts of cement
20~25 parts of silicon powder
20~30 parts of water
10~15 parts of additive
12~18 parts of modified fibre
2~5 parts of dispersing agent
10~12 parts of filler material
3~5 parts of glutaraldehyde
10~15 parts of slag
The additive the preparation method comprises the following steps:
Chitosan is mixed into swelling with water 1:5~1:8 in mass ratio, obtains swelling chitosan, swelling chitosan is gathered with shell
Carbohydrase 10:1~15:1 mixed enzymolysis in mass ratio, obtains Enzymatic Hydrolysis of Chitosan liquid, and Enzymatic Hydrolysis of Chitosan liquid and polyacrylamide are pressed matter
Amount is mixed than 8:1~10:1, and the water of 3~5 times of Enzymatic Hydrolysis of Chitosan liquid quality is added, and obtains additive；
The modified fibre the preparation method comprises the following steps:
Rice hull cellulose is moved into retort, under nitrogen protection, low temperature is carbonized at a slow speed, obtains hollow rice hull cellulose；It will be hollow
Rice hull cellulose and isocyanates 1:10~1:18 in mass ratio are mixed in beaker, are impregnated, filtering, the hollow fibre after must impregnating
Dimension；Doughnut after successively taking 15~25 parts of dippings according to parts by weight, 20~30 parts of urea, 80~100 parts of mass fractions
For 30% formalin, 3~5 parts of ethylene-maleic anhydrides, 2~4 parts of ammonium chlorides, 4~6 parts of resorcinols and 40~60 parts
Water, after mixing, constant temperature is stirred to react, then is filtered, dries to obtain modified fibre；
The well-cementing cement the preparation method comprises the following steps:
(1) each raw material is weighed by raw material composition；
(2) after mixing cement with water, silicon powder, additive, modified fibre, dispersing agent, glutaraldehyde, slag and filling is added
Material, is stirred, molding of vibrating obtains well-cementing cement after conserving.
The cement is any one in portland cement or aluminate cement.
The slag is any one in S105 grades of slags or S95 grades of slags.
The dispersing agent is any one in Dispersant MF or dispersing agent C F-40.
The filler material is any one in glass bead or titanium dioxide.
The beneficial effects of the present invention are:
(1) modified fibre is added when preparing well-cementing cement by the present invention, and the shell of one side modified fibre is through low temperature charcoal
Internal organic matter volatilization, the cuticula of outside covering are retained after change, hollow rice hull cellulose are obtained, firstly, hollow rice husk is fine
The hole generated in the fillable well-cementing cement forming process of the addition of dimension, increases well-cementing cement system to a certain extent
Consistency, to be that the mechanical property of product and anti-corrosion property can be improved, hollow rice hull cellulose surface has natural two
Silica cuticula may participate in the hydration reaction of cement after being added in well-cementing cement system, to further increase solid
The consistency of well water mudstone enables the anti-corrosion property of product and mechanical property to get a promotion；On the other hand, it is wrapped in hollow rice hull cellulose
Isocyanates is wrapped up in, in hydrated cementitious, forming process, due to external force and well-cementing cement itself system dilation
Effect makes hollow rice hull cellulose generate rupture, isocyanates outflow, and reacts with the water in system and generate carbon dioxide, due to
Calcium hydroxide is generated in cement hydration process, thus carbon dioxide can with calcium hydroxide reaction generate calcium carbonate, and due to
The capillary crack in well-cementing cement system can be filled, to make well-cementing cement system in the calcium carbonate small volume of generation
Consistency is further promoted, and the mechanical property of product and anti-corrosion property is enable to be improved；
(2) additive is added when preparing well-cementing cement by the present invention, firstly, containing activation chitosan in additive, it is living
Shielding metal ion can be chelated by changing chitosan, after being added in well-cementing cement system, can prevent system and it is extraneous into
Row ion exchange, secondly as activity improves chitosan after activation, is adding so that the anti-corrosion property of product be enable to be improved
It can react after entering into well-cementing cement system and polymerize in system, form certain network structure, to cement the well
The active force enhancing that each substance is shown in Behavior of Hardened Cement Paste system, consistency improve, and propose the mechanical property of product and antiseptic property
Height, furthermore due to also containing polyacrylamide in additive, polyacrylamide is good Water fixing agent, is being added to cementing concrete
The degree of hydration of cement in system can be improved after in stone system, and reduce water consumption, to make well-cementing cement system consistency
It improves, is improved the mechanical property of product.
Detailed description of the invention
Fig. 1 well-cementing cement compression strength testing result.
Specific embodiment
Chitosan and water 1:5~1:8 in mass ratio are mixed in beaker, mixing swelling obtains swelling chitosan, will be swollen
Chitosan is mixed with chitosan enzyme 10:1~15:1 in mass ratio, under conditions of temperature is 32~37 DEG C, is digested 4~6h, is obtained
Enzymatic Hydrolysis of Chitosan liquid and polyacrylamide 8:1~10:1 in mass ratio are mixed in flask by Enzymatic Hydrolysis of Chitosan liquid, and to flask
The middle water that 3~5 times of Enzymatic Hydrolysis of Chitosan liquid quality is added tests the speed flask immigration digital display constant temperature blender with magnetic force, in temperature be 40
It~55 DEG C, under conditions of revolving speed is 300~360r/min, is stirred, obtains additive；Rice hull cellulose is moved into retort, with
The rate of 50~80mL/min is passed through nitrogen into furnace, under nitrogen protection, is heated up with the heating rate of 0.4~0.7 DEG C/min
To 460~490 DEG C, 4~6h of insulation reaction obtains hollow rice hull cellulose, by hollow rice hull cellulose and isocyanates in mass ratio 1:
10~1:18 is mixed in beaker, impregnates 45~70min, filtering, and the doughnut after must impregnating successively takes according to parts by weight
Doughnut after 15~25 parts of dippings, 20~30 parts of urea, 80~100 parts of mass fractions are 30% formalin, 3~5 parts of second
Alkene-maleic anhydride, 2~4 parts of ammonium chlorides, 4~6 parts of resorcinols and 40~60 parts of water, after mixing in temperature be 50~60
DEG C, under the conditions of revolving speed is 300~500r/min, constant temperature is stirred to react 3~5h, then is filtered, dries to obtain modified fibre；By weight
Number meter successively weighs 50~70 parts of cement, and 20~25 parts of silicon powders, 20~30 parts of water, 10~15 parts of additives, 12~18 parts change
Property fiber, 2~5 parts of dispersing agents, 3~5 parts of glutaraldehydes, cement and water are added for 10~15 parts of slags and 10~12 parts of filler materials
Stirrer for mixing, and silicon powder is successively added into blender, additive, modified fibre, dispersing agent, glutaraldehyde and are filled out slag
Charge is 90~110r/min in revolving speed, under conditions of temperature is 50~60 DEG C, after being stirred 8~10min, vibrate 14~
20 times, molding obtains pretreatment well-cementing cement, by pretreatment well-cementing cement under the conditions of being protected from light, natural curing 7~9 days, obtains
Well-cementing cement.The cement is any one in portland cement or aluminate cement.The slag be S105 grades of slags or
Any one in S95 grades of slags.The dispersing agent is any one in Dispersant MF or dispersing agent C F-40.The filler material is
Any one in glass bead or titanium dioxide.
Example 1
Chitosan and water 1:8 in mass ratio are mixed in beaker, mixing swelling obtains swelling chitosan, and swelling shell is gathered
Sugar is mixed with chitosan enzyme 15:1 in mass ratio, under conditions of temperature is 37 DEG C, is digested 6h, Enzymatic Hydrolysis of Chitosan liquid is obtained, by shell
Glycan enzymolysis liquid and polyacrylamide 10:1 in mass ratio are mixed in flask, and Enzymatic Hydrolysis of Chitosan liquid quality is added into flask
5 times of water tests the speed flask immigration digital display constant temperature blender with magnetic force, in temperature be 55 DEG C, under conditions of revolving speed is 360r/min,
It is stirred, obtains additive；Rice hull cellulose is moved into retort, nitrogen is passed through into furnace with the rate of 80mL/min, in nitrogen
Under protection, 490 DEG C are warming up to the heating rate of 0.7 DEG C/min, insulation reaction 6h obtains hollow rice hull cellulose, by hollow rice husk
Fiber and isocyanates 1:18 in mass ratio are mixed in beaker, impregnate 70min, filtering, the doughnut after must impregnating, by weight
Amount number meter successively takes the doughnut after 25 parts of dippings, 30 parts of urea, and 100 parts of mass fractions are 30% formalin, 5 parts of second
Alkene-maleic anhydride, 4 parts of ammonium chlorides, 6 parts of resorcinols and 60 parts of water, after mixing in temperature be 60 DEG C, revolving speed 500r/
Under the conditions of min, constant temperature is stirred to react 5h, then is filtered, dries to obtain modified fibre；According to parts by weight, 70 parts of water are successively weighed
Mud, 25 parts of silicon powders, 30 parts of water, 15 parts of additives, 18 parts of modified fibres, 5 parts of dispersing agents, 5 parts of glutaraldehydes, 15 parts of slags and 12 parts
Cement and water are added stirrer for mixing, and silicon powder are successively added into blender by filler material, additive, modified fibre, point
Powder, glutaraldehyde, slag and filler material, in revolving speed be 110r/min, temperature be 60 DEG C under conditions of, after being stirred 10min,
It vibrates 20 times, forms, obtain pretreatment well-cementing cement, by pretreatment well-cementing cement under the conditions of being protected from light, natural curing 9 days,
Obtain well-cementing cement.The cement is portland cement.The slag is S105 grades of slags.The dispersing agent is Dispersant MF.
The filler material is glass bead.
Example 2
Chitosan and water 1:8 in mass ratio are mixed in beaker, mixing swelling obtains swelling chitosan, and swelling shell is gathered
Sugar is mixed with chitosan enzyme 15:1 in mass ratio, under conditions of temperature is 37 DEG C, is digested 6h, Enzymatic Hydrolysis of Chitosan liquid is obtained, by shell
Glycan enzymolysis liquid and polyacrylamide 10:1 in mass ratio are mixed in flask, and Enzymatic Hydrolysis of Chitosan liquid quality is added into flask
5 times of water tests the speed flask immigration digital display constant temperature blender with magnetic force, in temperature be 55 DEG C, under conditions of revolving speed is 360r/min,
It is stirred, obtains additive；Rice hull cellulose is moved into retort, nitrogen is passed through into furnace with the rate of 80mL/min, in nitrogen
Under protection, 490 DEG C, insulation reaction 6h are warming up to the heating rate of 0.7 DEG C/min, obtains hollow rice hull cellulose to get modified fine
Dimension；According to parts by weight, 70 parts of cement are successively weighed, 25 parts of silicon powders, 30 parts of water, 15 parts of additives, 18 parts of modified fibres, 5 parts
Stirrer for mixing is added in cement and water by dispersing agent, 5 parts of glutaraldehydes, 15 parts of slags and 12 parts of filler materials, and successively to stirring
Silicon powder, additive, modified fibre, dispersing agent, glutaraldehyde, slag and filler material are added in machine, in revolving speed be 110r/min, temperature
It under conditions of 60 DEG C, after being stirred 10min, vibrates 20 times, forms, obtain pretreatment well-cementing cement, pretreatment is cemented the well
Behavior of Hardened Cement Paste natural curing 9 days, obtains well-cementing cement under the conditions of being protected from light.The cement is portland cement.The slag is
S105 grades of slags.The dispersing agent is Dispersant MF.The filler material is glass bead.
Example 3
Polyacrylamide and water 1:2 in mass ratio are mixed in flask, the flask immigration digital display constant temperature magnetic force that tests the speed is stirred
Device is mixed, is 55 DEG C in temperature, under conditions of revolving speed is 360r/min, is stirred, obtains additive；Rice hull cellulose is moved into and is carbonized
Furnace is passed through nitrogen into furnace with the rate of 80mL/min, under nitrogen protection, is warming up to 490 with the heating rate of 0.7 DEG C/min
DEG C, insulation reaction 6h obtains hollow rice hull cellulose, and hollow rice hull cellulose and isocyanates 1:18 in mass ratio are mixed in beaker
In, 70min is impregnated, is filtered, the doughnut after must impregnating, the doughnut after successively taking 25 parts of dippings according to parts by weight,
30 parts of urea, 100 parts of mass fractions are 30% formalin, 5 parts of ethylene-maleic anhydrides, 4 parts of ammonium chlorides, 6 parts of isophthalic two
Phenol and 60 parts of water, after mixing in temperature be 60 DEG C, revolving speed be 500r/min under the conditions of, constant temperature is stirred to react 5h, then is filtered, done
It is dry to obtain modified fibre；According to parts by weight, 70 parts of cement are successively weighed, 25 parts of silicon powders, 30 parts of water, 15 parts of additives, 18 parts change
Property fiber, 5 parts of dispersing agents, 5 parts of glutaraldehydes, stirrer for mixing is added in cement and water by 15 parts of slags and 12 parts of filler materials, and
Silicon powder, additive, modified fibre, dispersing agent, glutaraldehyde, slag and filler material are successively added into blender, is in revolving speed
110r/min after being stirred 10min, vibrates 20 times under conditions of temperature is 60 DEG C, forms, obtains pretreatment well-cementing cement,
By pretreatment well-cementing cement under the conditions of being protected from light, natural curing 9 days, well-cementing cement is obtained.The cement is portland cement.
The slag is S105 grades of slags.The dispersing agent is Dispersant MF.The filler material is glass bead.
Example 4
Chitosan and water 1:8 in mass ratio are mixed in beaker, mixing swelling obtains swelling chitosan, and swelling shell is gathered
Sugar is mixed with chitosan enzyme 15:1 in mass ratio, under conditions of temperature is 37 DEG C, is digested 6h, Enzymatic Hydrolysis of Chitosan liquid is obtained, by shell
Glycan enzymolysis liquid and water 1:5 in mass ratio are mixed in flask, and flask immigration digital display is tested the speed constant temperature blender with magnetic force, Yu Wendu
It is 55 DEG C, under conditions of revolving speed is 360r/min, is stirred, obtains additive；Rice hull cellulose is moved into retort, with 80mL/
The rate of min is passed through nitrogen into furnace, under nitrogen protection, is warming up to 490 DEG C with the heating rate of 0.7 DEG C/min, heat preservation is anti-
6h is answered, hollow rice hull cellulose is obtained, hollow rice hull cellulose and isocyanates 1:18 in mass ratio are mixed in beaker, is impregnated
70min, filtering, the doughnut after must impregnating, the doughnut after successively taking 25 parts of dippings according to parts by weight, 30 parts of urine
Element, 100 parts of mass fractions are 30% formalin, 5 parts of ethylene-maleic anhydrides, 4 parts of ammonium chlorides, 6 parts of resorcinols and 60
Part water in temperature is 60 DEG C after mixing, and under the conditions of revolving speed is 500r/min, constant temperature is stirred to react 5h, then is filtered, dries to change
Property fiber；According to parts by weight, 70 parts of cement are successively weighed, 25 parts of silicon powders, 30 parts of water, 15 parts of additives, 18 parts of modified fibres,
Stirrer for mixing is added in cement and water by 5 parts of dispersing agents, 5 parts of glutaraldehydes, 15 parts of slags and 12 parts of filler materials, and successively to
Silicon powder, additive, modified fibre, dispersing agent, glutaraldehyde, slag and filler material are added in blender, in revolving speed be 110r/min,
It under conditions of temperature is 60 DEG C, after being stirred 10min, vibrates 20 times, forms, obtain pretreatment well-cementing cement, will pre-process
Well-cementing cement natural curing 9 days, obtains well-cementing cement under the conditions of being protected from light.The cement is portland cement.The slag
For S105 grades of slags.The dispersing agent is Dispersant MF.The filler material is glass bead.
Comparative example: the well-cementing cement of Suzhou engineering material Co., Ltd production.
The resulting well-cementing cement of example 1 to 4 and comparative example product are subjected to performance detection, the specific detection method is as follows:
1. mechanical property: preparing cement slurry referring to GB/T19139, sample conserves under 90 DEG C, 21MPa water bath condition
28d.Behavior of Hardened Cement Paste compression strength and tensile strength are measured with electronics hydraulic dynamometer；Behavior of Hardened Cement Paste flexural strength electric bending testing
Machine measurement；
2. anti-corrosion property energy: according to the corrosive concentration of oil-gas reservoir well stream object, (hydrogen sulfide mass concentration is 71~188g/
cm3；Carbon dioxide volume fraction is 0.87%~27.6%), its smallest concentration is amplified 5000 times respectively, is prepared into corrosion
Liquid.The cement slurry prepared by APISPEC10 is placed in die trial, is placed in high temperature and pressure protective cauldron and conserves 48h, is taken out de-
Mould.The cement briquette for having prepared and having numbered and corrosive medium are put into etcher again, observe pressure, the temperature of etcher at any time
Degree changes and adjusts in time, corrodes 30d, measures the corrosion depth of corrosion sample；Corrosion depth is bigger, then anti-corrosion property can be poorer.
The specific testing result of mechanical property is shown in Detailed description of the invention.
The specific testing result of anti-corrosion property energy is as shown in table 1:
Table 1
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Corrosion depth/mm | 1.1 | 1.3 | 2.1 | 1.9 | 3.8 |
By Detailed description of the invention Fig. 1 and 1 testing result of table it is found that technical solution of the present invention preparation well-cementing cement have both it is excellent
Mechanical property and the characteristics of anti-corrosion property energy, have broad prospects in the development of bored material industry.
Claims (5)
1. a kind of well-cementing cement, it is characterised in that: be made of the raw material of following parts by weight:
50~70 parts of cement
20~25 parts of silicon powder
20~30 parts of water
10~15 parts of additive
12~18 parts of modified fibre
2~5 parts of dispersing agent
10~12 parts of filler material
3~5 parts of glutaraldehyde
10~15 parts of slag
The additive the preparation method comprises the following steps:
Chitosan is mixed into swelling with water 1:5~1:8 in mass ratio, obtains swelling chitosan, by swelling chitosan and chitosan enzyme
10:1~15:1 mixed enzymolysis in mass ratio obtains Enzymatic Hydrolysis of Chitosan liquid, in mass ratio with polyacrylamide by Enzymatic Hydrolysis of Chitosan liquid
8:1~10:1 mixing, and the water of 3~5 times of Enzymatic Hydrolysis of Chitosan liquid quality is added, obtain additive；
The modified fibre the preparation method comprises the following steps:
Rice hull cellulose is moved into retort, under nitrogen protection, 460 are warming up to the heating rate of 0.4~0.7 DEG C/min~
490 DEG C, 4~6h of insulation reaction charing obtains hollow rice hull cellulose；By hollow rice hull cellulose and isocyanates 1:10 in mass ratio~
1:18 is mixed in beaker, is impregnated, filtering, the doughnut after must impregnating；15~25 parts of dippings are successively taken according to parts by weight
Doughnut afterwards, 20~30 parts of urea, 80~100 parts of mass fractions are 30% formalin, 3~5 parts of ethylene-maleics two
Acid anhydrides, 2~4 parts of ammonium chlorides, 4~6 parts of resorcinols and 40~60 parts of water, after mixing, constant temperature is stirred to react, then is filtered, done
It is dry to obtain modified fibre；
The well-cementing cement the preparation method comprises the following steps:
(1) each raw material is weighed by raw material composition；
(2) after mixing cement with water, silicon powder, additive, modified fibre, dispersing agent, glutaraldehyde, slag and filler material is added,
It is stirred, molding of vibrating obtains well-cementing cement after conserving.
2. a kind of well-cementing cement according to claim 1, it is characterised in that: the cement is portland cement or aluminic acid
Any one in salt cement.
3. a kind of well-cementing cement according to claim 1, it is characterised in that: the slag is S105 grades of slags or S95
Any one in grade slag.
4. a kind of well-cementing cement according to claim 1, it is characterised in that: the dispersing agent is Dispersant MF or dispersion
Any one in agent CF-40.
5. a kind of well-cementing cement according to claim 1, it is characterised in that: the filler material is glass bead or dioxy
Change any one in titanium.
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