CN101456931B - Synthesis of polymer oil well cement filtrate loss reduction additive and synthetic method thereof and application - Google Patents
Synthesis of polymer oil well cement filtrate loss reduction additive and synthetic method thereof and application Download PDFInfo
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Abstract
The invention relates to a synthetic polymer oil well cement filtrate reducer and a synthetic method thereof. The synthetic method comprises the following steps: a) preparing a raw material aqueous solution containing a first monomer selecting from 2-acryamide-2-methyl propanesulfonic acid, vinyl sulfonic acid or methacrylic acid, a second monomer selecting from N, N- dimethylacrylamide, acrylamide or N, N-diethylacrylamide, a third monomer selecting from maleic anhydride, maleic acid or fumaric acid, and a first regulator selecting from sodium allylsulfonate, dodecyl mercaptan and methyl sodium allylsulfonate, wherein the weight portion ratio of the first monomer to the second monomer to the third monomer to the first regulator is 65 to 95 portions: 1 to 30 portions: 1 to 5 portions: 0.01 to 5 portions; and b) adding an initiator, and heating up the raw material aqueous solution to a reaction temperature so as to carry out the polyreaction on the raw material aqueous solution. The synthetic polymer oil well cement filtrate reducer has good filtrate reduction performance, good temperature and salt resistance, and wide ambient temperature acclimation. The synthetic polymer oil well cement filtrate reducer can be used for an oil well cement slurry system, in particular for high temperature well cementing or seawater cementing.
Description
Technical field
The present invention relates to a kind of oil-well cement filtrate reducer and compound method thereof, especially a kind of synthetic polymer oil well cement filtrate loss reduction additive and compound method thereof.
Background technology
At present, the exploratory development of oil constantly develops to deep-sea, bad ground, deep-well and ultra deep well direction.Along with the also raising rapidly of increase well temperature of well depth, the drilling strata situation is also complicated more, such as there being highly mineralized formation brines etc.Simultaneously, the seawater mortar architecture is actively being promoted in marine well cementation.Therefore, to the cementing slurry admixture, especially the requirement of oil-well cement filtrate reducer is improving constantly, and need possess good temperature resistant antisalt performance.
At present, oil-well cement filtrate reducer commonly used mainly contains two big types, i.e. microparticle material water retaining and water-soluble polymer water retaining.The water-soluble polymer water retaining comprises natural polymer and modification class water retaining and synthetic polymer class water retaining again.
Synthetic polymer class water retaining is the water retaining hot of research and development, constantly has new kind to release both at home and abroad.Synthetic polymer class water retaining is generated by the monomer copolymerization more than two kinds usually, and anionic monomer commonly used has: 2-acrylamido-2-methyl propane sulfonic acid (AMPS), vinylformic acid (AA), methylacrylic acid, methylene-succinic acid etc.; Non-ionic monomer has: acrylic amide (AM), N; N-DMAA (NNDMA), N, N-diethylammonium acrylic amide, N-methyl-N-vinyl acetamide, N-vinyl-2-Pyrrolidone, divinyl, methylvinylether, methacrylic ester, MALEIC ANHYDRIDE, vinylbenzene, vinyl imidazole etc.; Cationic monomer has: 3-USAF RH-1 oxygen oxypropyl trimethyl ammonium chloride etc.
One of research and development trend of synthetic polymer oil well cement filtrate loss reduction additive develops to high temperature resistant, anti-salt, anti-hydrolysis direction exactly, with the needs that adapt to high temperature, high pressure, the well cementation of high salinity stratum and satisfy seawater prepared bentonite drilling fluid.At present, temperature resistant antisalt property synthetic polymer class water retaining mainly is to be basic synthetic copolymer product with modified propylene amides monomer.
People (Well cement additives such as Halliburton Larry S.Eoff in 2004; Compositonand methods; US6822061; 2004.11) issued a kind of terpolymer water retaining, first monomer of this multipolymer selects one from 2-acrylamido-2-methyl propane sulfonic acid, 2-allyloxy-2-hydroxy-propanesulfonic acid, vinyl sulfonic acid; Second monomer selects one from N in N-DMAA, acrylic amide, N-vinyl-2-Pyrrolidone, N-vinyl acetamide, the vinyl cyanide; The 3rd monomer is from bromide, muriate or the iodide (C of 16-22 carbon dimethylaminopropyl USAF RH-1
16-C
22DMAPMA), the bromide of 16-22 carbon dimethylaminopropyl methacrylic ester, muriate or iodide (C
16-C
22DMAMAC) select one in.Typical products AMPS/NNDMA/C
16DMAPMA (bromination hexadecyldimethyl benzyl ammonium aminopropyl USAF RH-1), there are good heatproof, anti-salt and filtrate-loss control ability in suitable molecular weight 7.5～300,000.Sample adds weight range 0.1～2%, and 60 ℃ of API WLes are that 38ml (0.6% dosage), 82.2 ℃ are 45ml (0.8% dosage).
Summary of the invention
The compound method that the purpose of this invention is to provide a kind of synthetic polymer oil well cement filtrate loss reduction additive.Another object of the present invention provides a kind of synthetic polymer oil well cement filtrate loss reduction additive.A further object of the invention is that synthetic polymer oil well cement filtrate loss reduction additive of the present invention is applied in the oil well cement slurry system, especially is applied in hot hole well cementation or the marine well cementation.
For achieving the above object, the invention provides a kind of compound method of synthetic polymer oil well cement filtrate loss reduction additive, said compound method comprises:
A) the preparation raw material aqueous solution, said aqueous solution of raw material comprise first monomer, second monomer, the 3rd monomer and first regulator, wherein
Said first monomer is selected from 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid and methylacrylic acid;
Said second monomer is selected from N, N-DMAA, acrylic amide and N, N-diethylammonium acrylic amide;
Said the 3rd monomer is selected from maleic anhydride, toxilic acid and fumaric acid;
Said first regulator is selected from sodium allylsulfonate, lauryl mercaptan and methylpropene sodium sulfonate;
Ratio of weight and number between said first monomer, said second monomer, said the 3rd monomer and said first regulator is 65～95 parts: 1～30 part: 1～5 part: 0.01～5 part of part.
And
B) employing comprises the solution polymerization condition that is warming up to temperature of reaction, adds initiator, and aqueous solution of raw material is reacted.
In compound method of the present invention, the ratio of weight and number between said first monomer, said second monomer, said the 3rd monomer and said first regulator is preferably 71～91 parts: 2～25 parts: 2～3 parts: 0.1～1.5 part.
In compound method of the present invention, said first monomer, said second monomer and the said the 3rd monomeric weight summation account for 10～30% of said aqueous solution of raw material weight, preferably, and 20～25%.The weight content of said first regulator in said aqueous solution of raw material is 0.01%～1%.
In compound method of the present invention, said aqueous solution of raw material in a) also comprises second regulator, and said second regulator is selected from YD 30, EDTA Disodium, tetrasodium ethylenediamine tetraacetate and N,N methylene bis acrylamide.The weight content of said second regulator in said aqueous solution of raw material is 0.01～0.1%.
In compound method of the present invention, said aqueous solution of raw material in a) also comprises the pH regulator agent, and said pH regulator agent is selected from sodium hydroxide, Pottasium Hydroxide, sodium hydrogencarbonate, yellow soda ash, hydrochloric acid, formic acid, acetate and propionic acid.Said pH regulator agent transfers to said aqueous solution of raw material pH value near neutral.
In compound method of the present invention, said initiator is a radical initiator, preferably ammonium persulphate or Sodium Persulfate.Said initiator accounts for 0.1～1% of said first monomer, said second monomer and the said the 3rd monomeric weight summation.
In compound method of the present invention, said b) step also is included in and adds before or after the initiator, makes said aqueous solution of raw material place inert gas atmosphere.
In compound method of the present invention, said b) temperature of reaction in is 40 ℃ to 85 ℃, preferably 55 ℃ to 70 ℃.
The present invention also provides according to above-mentioned compound method institute synthetic synthetic polymer oil well cement filtrate loss reduction additive.
The present invention also provides the application of above-mentioned synthetic polymer oil well cement filtrate loss reduction additive in the oil well cement slurry system in addition, preferably, and the application in hot hole well cementation or marine well cementation.
Synthetic polymer class water retaining mainly is to lean on adsorption to reduce the cement slurry water loss amount.The acrylic amide high adsorption capacity, good water solubility is used for the adsorption function that the synthetic polymer water retaining can guarantee that polymkeric substance is powerful, and the aggregated(particle)structure of control mortar architecture reduces its WL.In addition, the acrylamide polymerization activity is good, is easy to control, can obtain the suitable desired molecular weight of water retaining.Similarly, also can select N, N-DMAA or N, N-diethylammonium acrylic amide.But; Single SEPIGEL 305 temperature resistant antisalt property is poor; Therefore the present invention introduces and has the monomer that sedimentary strong hydrability anionic group does not take place with divalent ion; Have the bigger side group of volume and suppress the violent decline of the macromole ball of string size that inorganic salt cause, or have sulfonic high reactivity monomer and improve anti-divalence of heatproof and high volence metal ion ability to improve the macromole chain rigidity.So the present invention's first monomer has been selected 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid or methylacrylic acid.In addition, contain two carboxylic acid groups in maleic anhydride, toxilic acid or the fumaric acid, be used for the synthetic of oil-well cement filtrate reducer, can increase aquation group and adsorptive power greatly,, improve the filtration reduction ability of polymkeric substance through absorption, bridge formation, gathering and aquation.
The total concn of reaction monomers influences polymerization rate and the dehydration function falls in product.Increase total monomer, speed of response is accelerated, and product viscosity increases.Total monomer can not be excessive, excessive easy generation gather cruelly or product viscosity excessive; Otherwise, then be prone to cause speed of reaction low excessively, product effective concentration reduces.Therefore the present invention preferably, first monomer, said second monomer and the said the 3rd monomeric weight summation account for 10～30% of aqueous solution of raw material weight described in a), more preferably, are 20～25%.
In said a) the preparation raw material aqueous solution, three kinds of monomers can also can adopt random order to add in the water dissolving successively to evenly simultaneously.Preferably, adopting the 3rd monomer, first monomer, the second monomeric order to add in the water successively dissolves.
In order to obtain the product that better falls the dehydration function of suitable molecular weight product, said a) middle aqueous solution of raw material also comprises first regulator.Said first regulator is selected from sodium allylsulfonate, lauryl mercaptan and methylpropene sodium sulfonate, more preferably, is sodium allylsulfonate.For different raw materials, the consumption of first regulator can be different, and preferably, the mass content of first regulator in aqueous solution of raw material is 0.01%～1%.First regulator can be arbitrarily with respect to first monomer, second monomer and the 3rd monomer dissolving order in water; It can be before three kinds of monomers be dissolved in the water, between or be dissolved in water afterwards, preferably before three kinds of monomers are dissolved in the water, just be dissolved in the water.
For obtaining to fall preferably the synthetic polymer class water retaining of dehydration function, of the present invention a) in ratio of weight and number between first monomer, second monomer, the 3rd monomer and first regulator be generally 65～95 parts: 1～30 part: 1～5 part: 0.01～5 part; Preferably 71～91 parts: 2～25 parts: 2～3 parts: 0.1～1.5 part.
Preferably, said a) middle aqueous solution of raw material also comprises second regulator.Second regulator can with calcium ion, mg ion or the analogue chelating in the water, perhaps can make reaction monomers partial cross-linked.Said second regulator is selected from YD 30, EDTA Disodium, tetrasodium ethylenediamine tetraacetate and N,N methylene bis acrylamide.Preferably, the weight content of described second regulator in aqueous solution of raw material is 0.01～0.1%.Second regulator can be arbitrarily with respect to first monomer, second monomer and the 3rd monomer dissolving order in water, it can be before three kinds of monomers be dissolved in the water, between or be dissolved in water afterwards, preferably before three kinds of monomers are dissolved in the water.
The monomeric activity of pH value influence of aqueous solution of raw material, and then influence product group ratio and molecular weight, finally can exert an influence to polymer performance.In the polyreaction that has AMPS to participate in; But but AMPS has good also copolymerization of polymerization activity autohemagglutination, and under sour environment, the product of reaction is unfavorable for WL control; Though and the WL control influence to product is little under alkaline environment; But alkaline environment makes the amide group in the product be prone to decomposes, emits ammonia, influences high molecular stability.So preferably, said a) middle aqueous solution of raw material also comprises the pH regulator agent, and aqueous solution of raw material is near neutral.The pH regulator agent can be pH regulator agent known or commonly used, includes but not limited to sodium hydroxide (NaOH), Pottasium Hydroxide, sodium hydrogencarbonate, yellow soda ash, hydrochloric acid (HCl), formic acid, acetate or propionic acid.Preferably, be sodium hydroxide or hydrochloric acid.
Compound method b of the present invention) employed initiator is a radical initiator that use always or known in, comprises peroxide initiator and redox initiation system.The example of such radical initiator includes but not limited to, the persulphate of Potassium Persulphate, ammonium persulphate, Sodium Persulfate for example, hydrogen peroxide, and the hydroperoxide of isopropyl benzene hydroperoxide for example.Preferably use ammonium persulphate or Sodium Persulfate among the present invention.The add-on of radical initiator influences the size of polymerization rate and molecular weight of product.When the radical initiator add-on was big, the radical of generation was many, and it is many to cause point, and speed of response is fast, and the molecular weight of product is less.Otherwise, radical initiator add-on hour, the radical of generation is few, and it is few to cause point, and speed of response is slow, and the molecular weight of product is big.At compound method b of the present invention) in carry out in order to make to be reflected under the suitable speed; Obtain the suitable polymkeric substance oil-well cement filtrate reducer of molecular weight size, preferably initiator add-on scope is to account for 0.1～1% of said first monomer, said second monomer and the said the 3rd monomeric weight summation.
Compound method of the present invention can be carried out in commonly used or known conversion unit.The example of equipment includes but not limited to like this, the reaction kettle that comprises whipping appts, inflated with nitrogen device, heating unit and refrigerating unit commonly used.In compound method of the present invention, can before or after adding initiator, in conversion unit, charge into rare gas element, described rare gas element is in reaction, to keep inertia not participate in the gas that reacts, and includes but not limited to nitrogen or argon gas.
The temperature of reaction of compound method of the present invention can be to make said monomer polymerization reaction take place temperature usually, and temperature of reaction is little to the influence of product viscosity, and 40 ℃～85 ℃ all make reaction normally carry out, and synthesizes the product that viscosity is suitable, be easy to mix slurry.Preferably, temperature of reaction is 55 ℃～70 ℃.
In order to reduce the influence that residual monomer and residual monomer secondary reaction bring the water retaining performance as far as possible, the solution polymerization time of compound method of the present invention generally was controlled at more than 2 hours, preferably 4～6 hours.
The liquid product of reaction gained is the synthetic polymer oil well cement filtrate loss reduction additive, can directly use and need not to carry out aftertreatment again.Also can behind the polymerization reaction time of control, in the liquid product of gained, add a certain amount of blocker, oven dry is pulverized then, obtains the synthetic polymer oil well cement filtrate loss reduction additive of solid powdery.
Synthetic polymer oil well cement filtrate loss reduction additive of the present invention is through above-described compound method institute synthetic, density 1.05g/cm
3～1.10g/cm
3, 30 ℃～180 ℃ of Applicable temperature scopes have the temperature resistant antisalt performance, can be used for preparing the various cement slurry system, and cement slurry property is good, satisfies the cementing operation demand.
Synthetic polymer oil well cement filtrate loss reduction additive of the present invention can be applicable in the oil well cement slurry system, is particluarly suitable for using in hot hole well cementation or the marine well cementation.
The oil-well cement filtrate reducer synthetic process that is different from prior art on the present invention supplies raw materials.Compared with prior art, oil-well cement filtrate reducer of the present invention, filtrate-loss control can be good, and the temperature resistant antisalt performance is good, and is good with stratum and other admixture compatiblenesies, wide to the envrionment temperature adaptation, and good suspension stability and dissolution dispersity are arranged.Can be used in the various cement slurry system such as low density, high temperature, high-density.Can explain that through following table oil-well cement filtrate reducer of the present invention has filtrate-loss control ability and heat resistance preferably.
| Instance | The water retaining dosage | Probe temperature | API WL ml/30min |
| Embodiment 1 | 4％ | 60℃ | 26.2 |
| Embodiment 1 | 5％ | 120℃ | 32.8 |
| Embodiment 1 | 6％ | 150℃ | 56.2 |
| Comparative Examples 1 | 4％ | 60℃ | 35.2 |
| Comparative Examples 1 | 5％ | 120℃ | 82.6 |
| Comparative Examples 1 | 6％ | 150℃ | 182.0 |
Annotate: Comparative Examples 1 product is known, is the early production CG800L of COSL water retaining.Basic recipe is 100% cement+4% to 6% water retaining+fresh water.
Embodiment
To come further to set forth the present invention through following exemplary embodiment.
Embodiment 1
Building-up reactions is carried out in having the double-jacket formula enamel reaction still of steam heating, electronic stirring, and 39.58kg sodium hydroxide is dissolved in a certain amount of water in advance, and the stirring of sodium hydroxide limit is added on the limit, is made into sodium hydroxide solution.Open the reaction kettle whisking appliance, the sodium hydroxide solution that is made into is in advance pumped in the still.In reaction kettle, supply the water yield by calculated amount in table 1 stock chart.0.18kg YD 30 and 0.16kg sodium allylsulfonate are added in the reaction kettle, and dissolving evenly.The 4.30kg maleic anhydride is added in the reaction kettle, and dissolving evenly.Open cooling water circulationly, 189.70kg2-acrylamido-2-methyl propane sulfonic acid is slowly added in the reaction kettle, fully dissolving.Measure the pH value of solution value, regulate pH=6～7 with hydrochloric acid or sodium hydroxide.Close water coolant, with 16.07kgN, the N-DMAA adds reaction kettle, and dissolving is even, and aqueous solution of raw material preparation is so far accomplished.Under agitation begin to be warming up to 60 ± 2 ℃.Fill nitrogen 3～5min, the aqueous solution of the ammonium persulphate with 2.5% (being made into 2.5% aqueous solution with the 1.05kg ammonium persulphate) adds in the reaction kettle, continues inflated with nitrogen reaction 15～20 minutes.Stop inflated with nitrogen and close stirring, be incubated 3～4 hours, discharging.
Table 1 stock chart
| Raw material | Quality, kg |
| Zero(ppm) water or deionized water | 748.96 |
| Sodium hydroxide | 39.58 |
| YD 30 | 0.18 |
| Sodium allylsulfonate | 0.16 |
| Maleic anhydride | 4.30 |
| 2-acrylamido-2-methyl propane sulfonic acid | 189.70 |
| N, the N-DMAA | 16.07 |
| Ammonium persulphate | 1.05 |
The synthetic oil-well cement filtrate reducer is estimated its fundamental property indoor.Regulation according to API RP10B " oil well cement test recommended practice " the 22nd edition 1997 is tested; Sample thief is mixed with grout by different dosages and Shandong G level oil well cement and tap water in the synthetic oil-well cement filtrate reducer; Measure its rheological property and dehydration performance and seen table 2; Grout multiviscosisty performance is seen table 3, and grout ultimate compression strength performance is seen table 4, and dehydration performance is seen table 5 under the differing temps.In the table 5, warm retardant in the CH211 representative, PR20L represents high temperature retarder, and SSA represents the hot strength stablizer.
Table 2 slurry flowing performance-changing and dehydration performance table
Table 3 grout multiviscosisty performance table
Table 4 grout ultimate compression strength performance table
Cement slurry property under table 5 differing temps
| Sequence number | The grout prescription | Temperature ℃ | Density g/cm 3 | API WL ml | Thickening time min | 24h ultimate compression strength MPa |
| 1 | 100% cement+4% sample | 60 | 1.9 | 19.1 | ||
| 2 | 100% cement+4% sample | 90 | 1.9 | 25.6 | 144 | 21.4 |
| 3 | 100% cement+4% sample+0.5%CH211 | 90 | 1.9 | 22.8 | 374 | 20.7 |
| 4 | 100% cement+35%SSA+6.67% sample+1.67%PR20L | 120 | 1.9 | 27.0 | 252 | 21.2/90℃ |
| 5 | 100% cement+35%SSA+6.67% sample+1.67%PR20L | 150 | 1.9 | 34.0 | 125 | |
| 6 | 100% cement+35%SSA+6.67% sample+2.5%PR20L | 180 | 1.9 | 34.8 | 217 | |
| 7 | 100% cement+53.7% saturated brine+4% sample | 90 | 1.98 | 82ml |
Embodiment 2
Building-up reactions is carried out in having the double-jacket formula enamel reaction still of steam heating, electronic stirring, and 34.26kg sodium hydroxide is dissolved in a certain amount of water in advance, and the stirring of sodium hydroxide limit is added on the limit, is made into sodium hydroxide solution.Open the reaction kettle whisking appliance, the sodium hydroxide solution that is made into is in advance pumped in the still.In reaction kettle, supply the water yield by calculated amount in table 6 stock chart.0.18kg YD 30 and 2.95kg sodium allylsulfonate are added in the reaction kettle.Slowly add 6.44kg maleic anhydride, 154.54kg 2-acrylamido-2-methyl propane sulfonic acid, 53.66kg acrylic amide respectively, dissolving fully.Measure the pH value of solution value, regulate pH=6～7 with hydrochloric acid or sodium hydroxide.Under agitation begin to be warming up to 60 ± 2 ℃, fill nitrogen 5min, the aqueous solution of the ammonium persulphate with 2.5% (being made into 2.5% aqueous solution with the 1.29kg ammonium persulphate) adds in the reaction kettle, continues inflated with nitrogen reaction 15～20 minutes.Stop inflated with nitrogen and close stirring, be incubated 3～4 hours, discharging.
Table 6 stock chart
| Raw material | Quality, kg |
| Zero(ppm) water or deionized water | 746.69 |
| Sodium hydroxide | 34.26 |
| YD 30 | 0.18 |
| Sodium allylsulfonate | 2.95 |
| Maleic anhydride | 6.44 |
| 2-acrylamido-2-methyl propane sulfonic acid | 154.54 |
| Acrylic amide | 53.66 |
| Ammonium persulphate | 1.29 |
The synthetic oil-well cement filtrate reducer is estimated its fundamental property indoor.Regulation according to API RP10B " oil well cement test recommended practice " the 22nd edition 1997 is tested; Sample thief is mixed with grout by different dosages and cement and seawater in the synthetic oil-well cement filtrate reducer; Measured rheological property and the dehydration performance under the differing temps and seen table 7, and the thickening time under the differing temps and ultimate compression strength performance are seen table 8.
Rheology under table 7 differing temps, dehydration performance
Annotate: basic recipe is 100% cement+4% to 5% water retaining+seawater in the table 7, cement slurry density 1.9g/cm
3
Thickening time under table 8 differing temps, ultimate compression strength performance
| Sequence number | Water retaining sample dosage (BWOC) % | Density g/cm 3 | Experimental temperature ℃ | Thickening time min | Ultimate compression strength MPa |
| 1 | 4 | 1.9 | 60 | 102 | 21.2 |
| 2 | 4.5％ | 1.9 | 90 | 112 | 20.4 |
| 3 | 5％ | 1.9 | 120 | 87 | 24.2 |
Annotate: basic recipe is 100% cement+4% to 5% water retaining+seawater in the table 8.
Embodiment 3
Building-up reactions is carried out in having the double-jacket formula enamel reaction still of steam heating, electronic stirring, and 38.63kg sodium hydroxide is dissolved in a certain amount of water in advance, and the stirring of sodium hydroxide limit is added on the limit, is made into sodium hydroxide solution.Open the reaction kettle whisking appliance, the sodium hydroxide solution that is made into is in advance pumped in the still.In reaction kettle, supply the water yield by calculated amount in table 9 stock chart.0.18kg YD 30 and 1.85kg sodium allylsulfonate are added in the reaction kettle.Slowly add 4.20kg fumaric acid, 185.16kg2-acrylamido-2-methyl propane sulfonic acid, 5.31kg acrylic amide, 15.68kg N respectively, the N-DMAA, dissolving is fully.Measure the pH value of solution value, regulate pH=6～7 with hydrochloric acid or sodium hydroxide.Under agitation begin to be warming up to 65 ± 2 ℃, fill nitrogen 5min, the aqueous solution of the ammonium persulphate with 2.5% (being made into 2.5% aqueous solution with the 1.01kg ammonium persulphate) adds in the reaction kettle, continues inflated with nitrogen reaction 15～20 minutes.Stop inflated with nitrogen and close stirring, be incubated 3～4 hours.Add diphenol between 1.01kg at last, stirring and dissolving is even, discharging.
Table 9 stock chart
| Raw material | Quality, kg |
| Zero(ppm) water or deionized water | 746.96 |
| Sodium hydroxide | 38.63 |
| YD 30 | 0.18 |
| Sodium allylsulfonate | 1.85 |
| Fumaric acid | 4.20 |
| 2-acrylamido-2-methyl propane sulfonic acid | 185.16 |
| Acrylic amide | 5.31 |
| N, the N-DMAA | 15.68 |
| Ammonium persulphate | 1.01 |
| Between diphenol | 1.01 |
The synthetic oil-well cement filtrate reducer is estimated its fundamental property indoor.Regulation according to API RP10B " oil well cement test recommended practice " the 22nd edition 1997 is tested; Sample thief is mixed with grout by different dosages and cement and fresh water in the synthetic oil-well cement filtrate reducer; Measured rheological property and the dehydration performance under the differing temps and seen table 10, and the thickening time under the differing temps and ultimate compression strength performance are seen table 11.
Rheology under table 10 differing temps, dehydration performance
Annotate: basic recipe is 100% cement+4% to 5% water retaining+fresh water in the table 10.
Thickening time under table 11 differing temps, ultimate compression strength performance
| Sequence number | Water retaining sample dosage (BWOC) % | Density g/cm 3 | Experimental temperature ℃ | Thickening time min | Ultimate compression strength MPa |
| 1 | 4 | 1.9 | 60 | 98 | 20.9 |
| 2 | 4.5％ | 1.9 | 90 | 105 | 19.6 |
| 3 | 5％ | 1.9 | 120 | 79 | 22.3 |
Annotate: basic recipe is 100% cement+4% to 5% water retaining+fresh water in the table 11.
Embodiment 4
Building-up reactions is carried out in having the double-jacket formula enamel reaction still of steam heating, electronic stirring, and 39.58kg sodium hydroxide is dissolved in a certain amount of water in advance, and the stirring of sodium hydroxide limit is added on the limit, is made into sodium hydroxide solution.Open the reaction kettle whisking appliance, the sodium hydroxide solution that is made into is in advance pumped in the still.In reaction kettle, supply the water yield by calculated amount in table 12 stock chart.The 0.16kg sodium allylsulfonate is added in the reaction kettle, and dissolving evenly.The 4.30kg maleic anhydride is added in the reaction kettle, and dissolving evenly.Open cooling water circulationly, 189.70kg 2-acrylamido-2-methyl propane sulfonic acid is slowly added in the reaction kettle, fully dissolving.Measure the pH value of solution value, regulate pH=6～7 with hydrochloric acid or sodium hydroxide.Close water coolant, with 16.07kgN, the N-DMAA adds reaction kettle, and dissolving is even, and aqueous solution of raw material preparation is so far accomplished.Under agitation begin to be warming up to 60 ± 2 ℃.Fill nitrogen 3～5min, the aqueous solution of the ammonium persulphate with 2.5% (being made into 2.5% aqueous solution with the 1.05kg ammonium persulphate) adds in the reaction kettle, continues inflated with nitrogen reaction 15～20 minutes.Stop inflated with nitrogen and close stirring, be incubated 3～4 hours, discharging.
Table 12 stock chart
| Raw material | Quality, kg |
| Zero(ppm) water or deionized water | 748.96 |
| Sodium hydroxide | 39.58 |
| Sodium allylsulfonate | 0.16 |
| Maleic anhydride | 4.30 |
| 2-acrylamido-2-methyl propane sulfonic acid | 189.70 |
| N, the N-DMAA | 16.07 |
| Ammonium persulphate | 1.05 |
The synthetic oil-well cement filtrate reducer is estimated its fundamental property indoor.Regulation according to API RP10B " oil well cement test recommended practice " the 22nd edition 1997 is tested; Sample thief is mixed with grout by different dosages and cement and fresh water in the synthetic oil-well cement filtrate reducer, has measured the cement slurry property under the differing temps and has seen table 13.
Cement slurry property under table 13 differing temps
| Sequence number | Water retaining sample dosage (BWOC) % | Experimental temperature, ℃ | The API WL, ml | Thickening time, min | Ultimate compression strength, MPa |
| 1 | 4 | 60 | 32.4 | 102 | 19.5 |
| 2 | 4.5 | 90 | 35.6 | 107 | 20.4 |
| 3 | 5 | 120 | 48.2 | 89 | 23.6 |
Annotate: basic recipe is 100% cement+4% to 5% water retaining+fresh water in the table 13.
It is thus clear that through regulating the sample dosage, above-mentioned synthetic water retaining has good control dehydration performance when guaranteeing good rheological, the API WL can be controlled in the 50ml, and is easier to WL is dropped to below the 30ml.The synthetic water retaining is to not ultra slow setting of grout and blood coagulation enhancing effect, and along with the increase of sample dosage, the thickening time is influential slightly, but influence is little, in allowed band.The synthetic water retaining does not have adverse influence to the intensity of grout, and intensity level reaches the well cementation needs fully.The synthetic water retaining has good heat resistance and anti-salt property, at 180 ℃ with join with salt solution under the slurry, has all showed good filtrate-loss control ability.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Therefore; No matter from which point; Above-mentioned embodiment of the present invention all can only be thought can not limit the present invention to explanation of the present invention, and claims have been pointed out scope of the present invention, therefore; In implication suitable and any change in the scope, all think to be included in the scope of claims with claims of the present invention.
Claims (13)
1. one kind is used to cement the well with the compound method of the water retaining of grout, and said compound method comprises:
A) the preparation raw material aqueous solution, said aqueous solution of raw material comprise first monomer, second monomer, the 3rd monomer, first regulator and second regulator, wherein
Said first monomer is selected from 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid and methylacrylic acid;
Said second monomer is selected from N, N-DMAA, acrylic amide and N, N-diethylammonium acrylic amide;
Said the 3rd monomer is selected from maleic anhydride, toxilic acid and fumaric acid;
Said first regulator is selected from sodium allylsulfonate and methylpropene sodium sulfonate;
Said second regulator is selected from YD 30, EDTA Disodium and tetrasodium ethylenediamine tetraacetate;
Ratio of weight and number between said first monomer, said second monomer, said the 3rd monomer and said first regulator is 65～95 parts: 1～30 part: 1～5 part: 0.01～5 part,
The weight content of said second regulator in said aqueous solution of raw material is 0.01～0.1%;
And
B) employing comprises the solution polymerization condition that is warming up to temperature of reaction, adds initiator, and aqueous solution of raw material is reacted.
2. compound method according to claim 1, wherein said first monomer, said second monomer and the said the 3rd monomeric weight summation account for 10～30% of said aqueous solution of raw material weight.
3. compound method according to claim 2, wherein said first monomer, said second monomer and the said the 3rd monomeric weight summation account for 20～25% of said aqueous solution of raw material weight.
4. compound method according to claim 1, the weight content of wherein said first regulator in said aqueous solution of raw material is 0.01%～1%.
5. compound method according to claim 1; Wherein said aqueous solution of raw material in a) also comprises the pH regulator agent; Said pH regulator agent is selected from sodium hydroxide, Pottasium Hydroxide, sodium hydrogencarbonate, yellow soda ash, hydrochloric acid, formic acid, acetate and propionic acid, and said pH regulator agent transfers to said aqueous solution of raw material pH value near neutral.
6. compound method according to claim 1, wherein said initiator is a radical initiator.
7. compound method according to claim 6, wherein said radical initiator are ammonium persulphate or Sodium Persulfate.
8. compound method according to claim 1, wherein said initiator account for 0.1～1% of said first monomer, said second monomer and the said the 3rd monomeric weight summation.
9. the temperature of reaction compound method according to claim 1, wherein said b) is 40 ℃ to 85 ℃.
10. the temperature of reaction compound method according to claim 9, wherein said b) is 55 ℃ to 70 ℃.
11. compound method according to claim 1, the ratio of weight and number between wherein said first monomer, said second monomer, said the 3rd monomer and said first regulator is 71～91 parts: 2～25 parts: 2～3 parts: 0.1～1.5 part.
12. according to the water retaining that is used to cement the well of each described compound method institute synthetic in the claim 1 to 11 with grout.
13. the water retaining that is used for cementing the well with grout according to claim 12 is cemented the well or marine application of cementing the well at hot hole.
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: China Oilfield Services Limited Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: China Oilfield Services Limited Patentee before: China National Offshore Oil Corporation |