CN106279528A - Seawer system oil well cement dispersant and preparation method thereof - Google Patents
Seawer system oil well cement dispersant and preparation method thereof Download PDFInfo
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- CN106279528A CN106279528A CN201610650154.4A CN201610650154A CN106279528A CN 106279528 A CN106279528 A CN 106279528A CN 201610650154 A CN201610650154 A CN 201610650154A CN 106279528 A CN106279528 A CN 106279528A
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- oil well
- system oil
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- 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
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of seawer system oil well cement dispersant and preparation method thereof, it is by the tetra-kinds of monomer components of A, B, C, D ampholyte copolymer by aqueous solution polymerization, according to the mass fraction, component A 50 60 parts, B component 10 18 parts, component C 5 12 parts, D component 15 20 parts, reaction density is 15 22%, compares concentration for quality；The dispersant of the present invention can effectively control the impact on cement mortar mobility of the high volence metal ion in sea water, the most high temperature resistant, is particularly well-suited in marine casing and cementing, can gather materials on the spot, and seawater prepared bentonite drilling fluid reduces casing and cementing cost.
Description
Technical field
The present invention relates to cement dispersants, specifically, be a kind of seawer system oil well cement dispersant and preparation side thereof
Method.
Background technology
When sea water well cementing operation, due in sea water except containing substantial amounts of sodium chloride can make cement mortar produce coagulant, change
Thick phenomenon, simultaneously a large amount of high volence metal ion such as Mg present in sea water2+, Ca2+Deng, these ions can reduce cement mortar
Mobility so that it is viscosity and shear force rise, and greatly affect the rheological characteristic of cement mortar.Therefore the performance of conventional cement slurries is the most not
The related request of well cementing operation can be met, and fresh water reservoir storage is limited by space and load, often cannot meet large-scale simultaneously
Well cementing operation requirement.Therefore, if cement mortar can be prepared with sea water, it will bring the biggest economic benefit to casing and cementing.Cause
This, research and development one can be applicable to seawater prepared bentonite drilling fluid construction environment, improves sea water mortar architecture mobility, reduces operation pressure
Dispersant product, being not only convenient for gathering materials on the spot fundamentally solves platform fresh water inventory problem, can save a large amount of fresh water money simultaneously
Source, reduces well cementation cost.
At present, for Cementing engineering, existing polytype dispersant product, if lignosulfonates are casing and cementings
The most frequently used dispersant, such dispersant has certain sugar amount, so in addition to having peptizaiton, also having due to wherein remaining
Stronger deferred action, therefore uses temperature the most relatively low, not salt tolerant.Keto-aldehyde class dispersant is also to use in casing and cementing
Dispersant widely, but when such dispersant is applied at the scene, powder body dust causes toxicity the most floating time big, water-soluble, not salt tolerant,
Therefore, if conventional dispersant is in seawater mud, drag reduction dispersion efficiency declines, poor for applicability, can not solve sea water water
The flowability problem of mud.
Summary of the invention
The technical problem to be solved is to provide a kind of seawer system oil being applied in marine casing and cementing
Well cement dispersant and preparation method thereof, effectively controls the high volence metal ion impact on cement mortar mobility in sea water, resistance to height
Temperature, uses volume low.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: a kind of seawer system oil-well cement divides
Powder, dispersant is by the tetra-kinds of monomer components of A, B, C, D ampholyte copolymer by aqueous solution polymerization, by mass fraction
Meter, component A 50-60 part, B component 10-18 part, component C 5-12 part, D component 15-20 part, reaction density is 15-22%, for matter
Amount percent concentration；
Described component A is in 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid salt
A kind of or their mixture；
Described B component is acrylamide, N, a kind of in N-DMAA or their mixture；
Described component C is a kind of in acrylic acid, methacrylic acid or their mixture；
Described D component is dimethyl diallyl ammonium chloride.
Preferably, described component A is 2-acrylamide-2-methylpro panesulfonic acid, and B component is acrylamide；Component C is propylene
Acid.
The chain-transferring agent of polymerization is isopropanol, and the initiator of polymerization is azo-bis-isobutyrate hydrochloride, the terminator of polymerization
For sodium sulfite.
Described chain-transferring agent consumption is the 0.5%-1.0% of monomer gross mass, and initiator amount is monomer gross mass
1.5-2.0%, terminator consumption is the 1.0%-1.5% of monomer gross mass.
The preparation method of above-mentioned seawer system oil well cement dispersant, comprises the following steps: in reactor successively
Add component A, B component, D component and supply the water yield, making material dissolution uniform with 60-70 rev/min of speed stirring, be warming up to
60-65 DEG C, continue stirring logical nitrogen 30min, C group and chain-transferring agent are added reactor, is under agitation warming up to 70-75
DEG C, dropwise instill initiator solution, after 60-70 rev/min of speed constant temperature stirring 2h-3h, add terminator, be cooled to room
Temperature, dropwise dropping mass fraction be 30% sodium hydroxide solution regulation pH value to 7, obtain white or faint yellow dispersant liquid
Body, drying obtains dispersant powder body after pulverizing.
The invention has the beneficial effects as follows: the dispersant product that the present invention relates to belongs to ampholyte copolymer, contains in AMPS molecule
Sulfonic acid group, and there is good hydrophilic, hard water resistance property and heat-resisting quantity, active carbon-carbon double bond makes it have higher work
Property, easily it is copolymerized with monomer, containing quaternary amines in DMDAAC molecule, quaternary amine base and amide groups energy and cement granules
The negative charge on surface adsorbs, and sulfonic group and carboxyl can be with the Ca in sea water2+、Mg2+Formed Deng metal ion and well join
Position effect, plays absorption and scavenging action.Compared with single functional group anionic polymer, it can be in cement particle surface shape
Become firm adsorption layer, by sterically hindered effect, cement granules can be made well to be dispersed in water.Meanwhile, in the reaction, logical
Cross interpolation isopropanol and can control the viscosity of polymer molecular weight and product as chain-transferring agent.The present invention can effectively control sea water
The impact on cement mortar mobility of the middle high volence metal ion, high temperature resistant, use volume low, be particularly well-suited to marine casing and cementing,
Can gather materials on the spot seawater prepared bentonite drilling fluid, reduce casing and cementing cost.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail:
The seawer system oil well cement dispersant of the present invention, dispersant is to be passed through water by tetra-kinds of monomer components of A, B, C, D
The ampholyte copolymer of polymerisation in solution, according to the mass fraction, component A 50-60 part, B component 10-18 part, component C 5-12 part, D
Component 15-20 part, chain-transferring agent consumption is the 0.5%-1.0% of monomer gross mass, and initiator amount is monomer gross mass
1.5-2.0%, terminator consumption is the 1.0%-1.5% of monomer gross mass, and reaction density is 15-22%, for mass percent
Concentration.
The proportioning of reaction monomers and reaction density directly affect polymerization rate and product property, and reaction density is excessive,
Easily occur sudden and violent poly-or product viscosity is excessive, otherwise, too small, easily cause reaction rate low, product valid density reduces.
The consumption of initiator affects monomer conversion, and when initiator amount is too small, monomer can not react completely, and polymer
Molecular weight is excessive, plays a role affecting important group on main chain, and dispersive property is the highest.Initiator amount is excessive, and the degree of polymerization is low,
Polymer molecular weight is too small, and cement granules per surface area is accomplished by adsorbing more dispersant molecule, i.e. need relatively large dosage
Can be only achieved preferable dispersion effect, and the excessive response speed that also can make polymerization system of initiator amount is too fast, easily causes
Bumping, affects dispersive property and also increases application cost.Therefore, initiator optimum dose is the 1.5-2.0% of monomer gross mass.
The consumption of chain-transferring agent affects polymer chain length and viscosity, by adding appropriate chain-transferring agent, Collaborative Control
Polymer molecular weight and viscosity.
Feeding mode produces impact, the present invention to aspects such as polymerization rate, monomer conversion and molecular size ranges
The feeding mode used avoids polymerization activity big component C and self-polymeric reaction occurs so that remain too much in reaction system
Other monomers, affect dispersive property, and meanwhile, initiator uses the form of dropping so that in the condition that number of free radical is stable
Under, molecular weight distribution is narrower.
Preparation method: add component A, B component, D component in reactor successively and supply the water yield, with 60-70 rev/min
Speed stirring makes material dissolution uniform, is warming up to 60-65 DEG C, continues stirring logical nitrogen 30min, C group and chain-transferring agent is thrown
Add reactor, be under agitation warming up to 70-75 DEG C, dropwise instill initiator solution, about 1.5h and drip off, with 60-70 rev/min of clock rate
After degree constant temperature stirring 2h-3h, adding terminator, be cooled to room temperature, dropwise dropping mass fraction is the sodium hydroxide solution of 30%
Regulation pH value, to 7, obtains white or faint yellow dispersant liq, and drying obtains dispersant powder body after pulverizing.
Described component A is in 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid salt
A kind of or their mixture, more preferably component A is 2-acrylamide-2-methylpro panesulfonic acid (AMPS)；
Described B component is a kind of in acrylamide, N,N-DMAA or their mixture, more preferably B
Component is acrylamide (AM)；
Described component C is acrylic acid, methacrylic acid a kind of or their mixture, and more preferably component C is acrylic acid
(AA)；
Described D component is dimethyl diallyl ammonium chloride (DMDAAC)
Described polymerization chain transfer agents is isopropanol.
Described initiators for polymerization is azo-bis-isobutyrate hydrochloride (AIBA 2HCL), is a kind of water-soluble azo class
Initiator, has relatively low decomposition activation energy, and the initiator of residual does not affect the stability of polymer, and conventional in commercial production
Persulfuric acid salt, easily there is induced decomposition, and the persulfuric acid salt initiator of residual run into alkaline cement and can decompose release gas
Taste, has certain impact to application.
Described polyreaction terminator is sodium sulfite.
Embodiment 1
Sample 1 formula: 60.0 grams of 2-acrylamide-2-methylpro panesulfonic acids (AMPS), 15.0 grams of acrylamides (AM),
9.5 grams of acrylic acid (AA), 15.5 grams of dimethyl diallyl ammonium chlorides (DMDAAC), 1.5 grams of azo-bis-isobutyrate hydrochlorides
(AIBA 2HCL), 1.0 grams of sodium sulfitees, 0.5 gram of isopropanol, 396 grams of water.
Sample 2 formula: 55.0 grams of 2-acrylamide-2-methylpro panesulfonic acids (AMPS), 15.0 grams of acrylamides (AM),
10.0 grams of acrylic acid (AA), 20.0 grams of dimethyl diallyl ammonium chlorides (DMDAAC), 1.7 grams of azo-bis-isobutyrate hydrochlorides
(AIBA 2HCL), 1.25 grams of sodium sulfitees, 0.7 gram of isopropanol, 396.35 grams of water.
Sample 3 formula: 52.0 grams of 2-acrylamide-2-methylpro panesulfonic acids (AMPS), 18.0 grams of acrylamides (AM),
12.0 grams of acrylic acid (AA), 18.0 grams of dimethyl diallyl ammonium chlorides (DMDAAC), 1.85 grams of azo-bis-isobutyrate hydrochlorides
(AIBA 2HCL), 1.15 grams of sodium sulfitees, 0.8 gram of isopropanol, 396.2 grams of water.
Preparation method: select formula (1) or (2) or (3) one of which, add successively in reactor component A, B component,
D component also supplies the water yield, makes material dissolution uniform with 60-70 rev/min of speed stirring, is warming up to 60-65 DEG C, continues stirring also
Logical nitrogen 30min, adds reactor by C group and chain-transferring agent, is under agitation warming up to 70-75 DEG C, dropwise instills initiator molten
Liquid, about 1.5h drip off, and after 60-70 rev/min of speed constant temperature stirring 2h-3h, add terminator, are cooled to room temperature, dropwise drip
Add sodium hydroxide solution that mass fraction is 30% regulation pH value to 7, obtain water white transparency dispersant liq, after drying is pulverized
Obtain dispersant powder body.
The dispersant product indices of the present invention complies fully with People's Republic of China's oil and gas industry standard " oil
Well cement additive evaluation methodology third portion: drag reducer " indices requirement.In experiment, material composition all derives from city
Sell.
Embodiment 2
According to National Standard of the People's Republic of China GB/T 19139-2012 " oil-well cement test method " chapter 5 requirement
Method prepare sea water cement mortar.
Sea water cement mortar forms substantially: G class g cement 580g；Silica flour 174g；Micro-silicon 29g；Retarder 5.0g, sea water and cement
Dry ash mass ratio is 0.36.
(1) the rheological property evaluation of oil well cement dispersant sea water cement mortar of the present invention is applied
Want according to National Standard of the People's Republic of China GB/T 19139-2012 " oil-well cement test method " chapter 12
The method step asked, the above-mentioned sea water cement containing Different adding amount inventive dispersant (Example formulations (1)) that will be made into
Slurry is gradually warmed up to 85 DEG C of 30min the most continuously stirred by 27 ± 1 DEG C in normal pressure multiviscosity meter, pours six speed immediately after into and rotates glutinous
To graduation mark in degree meter specimen cup, the rheological parameter value of test slurry.The results are shown in Table 1.
The impact on sea water slurry flowing performance-changing of table 1 inventive dispersant
Conclusion: application inventive dispersant has preferable rheological property when 1.5% that volume is G class g cement quality,
Can effectively control high volence metal ion such as Mg2+, Ca2+Deng the impact on cement mortar mobility, use volume low, particularly suitable
In marine casing and cementing, seawater prepared bentonite drilling fluid, gather materials on the spot, reduce casing and cementing cost.
Embodiment described above is merely to illustrate technological thought and the feature of the present invention, in its object is to make this area
Skilled artisan will appreciate that present disclosure and implement according to this, it is impossible to only limit the patent model of the present invention with the present embodiment
Enclosing, what the most all disclosed spirit was made changes on an equal basis or modifies, and still falls in the scope of the claims of the present invention.
Claims (5)
1. a seawer system oil well cement dispersant, it is characterised in that dispersant is to be led to by tetra-kinds of monomer components of A, B, C, D
Cross the ampholyte copolymer of aqueous solution polymerization, according to the mass fraction, component A 50-60 part, B component 10-18 part, component C 5-12
Part, D component 15-20 part, reaction density is 15-22%, for mass percent concentration；
Described component A is the one in 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid salt
Or their mixture；
Described B component is acrylamide, N, a kind of in N-DMAA or their mixture；
Described component C is a kind of in acrylic acid, methacrylic acid or their mixture；
Described D component is dimethyl diallyl ammonium chloride.
Seawer system oil well cement dispersant the most according to claim 1, it is characterised in that described component A is 2-propylene
Amide groups-2-methyl propane sulfonic acid, B component is acrylamide；Component C is acrylic acid.
Seawer system oil well cement dispersant the most according to claim 1, it is characterised in that the chain-transferring agent of polymerization is different
Propanol, the initiator of polymerization is azo-bis-isobutyrate hydrochloride, and the terminator of polymerization is sodium sulfite.
Seawer system oil well cement dispersant the most according to claim 3, it is characterised in that described chain-transferring agent consumption is
The 0.5%-1.0% of monomer gross mass, initiator amount is the 1.5-2.0% of monomer gross mass, and terminator consumption is that monomer is total
The 1.0%-1.5% of quality.
5. the preparation method of the seawer system oil well cement dispersant as described in any one of claim 1-4, it is characterised in that
Comprise the following steps: in reactor, add component A, B component, D component successively and supply the water yield, with 60-70 rev/min of speed
Stirring makes material dissolution uniform, is warming up to 60-65 DEG C, continues stirring logical nitrogen 30min, C group and chain-transferring agent is added instead
Answer still, be under agitation warming up to 70-75 DEG C, dropwise instill initiator solution, with 60-70 rev/min of speed constant temperature stirring 2h-3h
After, add terminator, be cooled to room temperature, dropwise dropping mass fraction be 30% sodium hydroxide solution regulation pH value to 7, obtain
White or faint yellow dispersant liq, drying obtains dispersant powder body after pulverizing.
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| CN101631842A (en) * | 2007-01-11 | 2010-01-20 | 哈利伯顿能源服务公司 | Cement compositions comprising humic acid grafted fluid loss control additives and methods of using them |
| CN102241490A (en) * | 2011-04-20 | 2011-11-16 | 天津科力奥尔工程材料技术有限公司 | Oil well cement dispersant and preparation method thereof |
| CN102617811A (en) * | 2012-03-21 | 2012-08-01 | 陕西科技大学 | Preparation method of amphiprotic vinyl polymer concrete mud-resistant agent |
| CN104446101A (en) * | 2014-11-26 | 2015-03-25 | 中建商品混凝土有限公司 | Cation modified polycarboxylate superplasticizer and preparation method thereof |
| CN105601787A (en) * | 2015-12-24 | 2016-05-25 | 江苏苏博特新材料股份有限公司 | Method for preparing cement dispersant with both high water reduction effect and viscosity reduction effect |
-
2016
- 2016-08-08 CN CN201610650154.4A patent/CN106279528A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101631842A (en) * | 2007-01-11 | 2010-01-20 | 哈利伯顿能源服务公司 | Cement compositions comprising humic acid grafted fluid loss control additives and methods of using them |
| CN102241490A (en) * | 2011-04-20 | 2011-11-16 | 天津科力奥尔工程材料技术有限公司 | Oil well cement dispersant and preparation method thereof |
| CN102617811A (en) * | 2012-03-21 | 2012-08-01 | 陕西科技大学 | Preparation method of amphiprotic vinyl polymer concrete mud-resistant agent |
| CN104446101A (en) * | 2014-11-26 | 2015-03-25 | 中建商品混凝土有限公司 | Cation modified polycarboxylate superplasticizer and preparation method thereof |
| CN105601787A (en) * | 2015-12-24 | 2016-05-25 | 江苏苏博特新材料股份有限公司 | Method for preparing cement dispersant with both high water reduction effect and viscosity reduction effect |
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Application publication date: 20170104 |
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| WD01 | Invention patent application deemed withdrawn after publication |